Persistent photovoltage in methylammonium lead iodide perovskite solar cells

Open circuit voltage decay measurements are performed on methylammonium lead iodide (CH3NH3PbI3) perovskite solar cells to investigate the charge carrier recombination dynamics. The measurements are compared to the two reference polymer-fullerene bulk heterojunction solar cells based on P3HT:PC60BM and PTB7:PC70BM blends. In the perovskite devices, two very different time domains of the voltage decay are found, with a first drop on a short time scale that is similar to the organic solar cells. However, two major differences are also observed. 65-70% of the maximum photovoltage persists on much longer timescales, and the recombination dynamics are dependent on the illumination intensity.Comment: 5 pages, 3 figure

Photovoltaic Devices Using Sublimed Methylammonium Lead Iodide Perovskites: Long-Term Reproducible Processing

Fully evaporated solar cells using methylammonium iodide (MAI)-based perovskites can reach power conversion efficiencies exceeding 20%. An important point to advance perovskite photovoltaics is to ensure reproducibility from batch to batch. Sublimation control of organic ammonium halides is critical in achieving this for evaporated perovskite solar cells. Herein, a reproducible procedure for the coevaporation of PbI2 and MAI based on an evaporator chamber setup with only two quartz crystal microbalances (QCMs) is described. One QCM monitors exclusively the PbI2 precursor (PbI2-QCM) and the second QCM monitors the total amount of MAPbI3 mass reaching the substrates (MAPbI3-QCM). It is shown that the MAI evaporation can be reliably monitored, indirectly, through the MAPbI3-QCM. In this way, the fluctuating sublimation rates usually observed due to variations of MAI purity are avoided. This allows one to obtain consistently high-performing solar cells over a period of one and a half years

Shine bright or live long: substituent effects in [Cu(N^N)(P^P)]+-based light-emitting electrochemical cells where N^N is a 6-substituted 2,2'-bipyridine

We report [Cu(P^P)(N^N)][PF6] complexes with P^P = bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) and N^N = 6-methyl-2,2′-bipyridine (Mebpy), 6-ethyl-2,2′-bipyridine (Etbpy), 6,6′-dimethyl-2,2′-bipyridine (Me2bpy) or 6-phenyl-2,2′-bipyridine (Phbpy). The crystal structures of [Cu(POP)(Phbpy)][PF6]·Et2O, [Cu(POP)(Etbpy)][PF6]·Et2O, [Cu(xantphos)(Me2bpy)][PF6], [Cu(xantphos)(Mebpy)][PF6]·CH2Cl2·0.4Et2O, [Cu(xantphos)(Etbpy)][PF6]·CH2Cl2·1.5H2O and [Cu(xantphos)(Phbpy)][PF6] are described; each copper(I) centre is distorted tetrahedral. In the crystallographically determined structures, the N^N domain in [Cu(xantphos)(Phbpy)]+ and [Cu(POP)(Phbpy)]+ is rotated ∼180° with respect to its orientation in [Cu(xantphos)(Mebpy)]+, [Cu(POP)(Etbpy)]+ and [Cu(xantphos)(Etbpy)]+; in each complex containing xantphos, the xanthene ‘bowl’ retains the same conformation in the solid-state structures. The two conformers resulting from the 180° rotation of the N^N ligand were optimized at the B3LYP-D3/(6-31G**+LANL2DZ) level and are close in energy for each complex. Variable temperature NMR spectroscopy evidences the presence of two conformers of [Cu(xantphos)(Phbpy)]+ in solution which are related by inversion of the xanthene unit. The complexes exhibit MLCT absorption bands in the range 378 to 388 nm, and excitation into each MLCT band leads to yellow emissions. Photoluminescence quantum yields (PLQYs) increase from solution to thin-film and powder; the highest PLQYs are observed for powdered [Cu(xantphos)(Mebpy)][PF6] (34%), [Cu(xantphos)(Etbpy)][PF6] (37%) and [Cu(xantphos)(Me2bpy)][PF6] (37%) with lifetimes of 9.6–11 μs. Density functional theory calculations predict that the emitting triplet (T1) involves an electron transfer from the Cu–P^P environment to the N^N ligand and therefore shows a 3MLCT character. T1 is calculated to be ∼0.20 eV lower in energy than the first singlet excited state (S1). The [Cu(P^P)(N^N)][PF6] ionic transition-metal (iTMC) complexes were tested in light-emitting electrochemical cells (LECs). Turn-on times are fast, and the LEC with [Cu(xantphos)(Me2bpy)][PF6] achieves a maximum efficacy of 3.0 cd A−1 (luminance = 145 cd m−2) with a lifetime of 1 h; on going to the [Cu(xantphos)(Mebpy)][PF6]-based LEC, the lifetime exceeds 15 h but at the expense of the efficacy (1.9 cd A−1). The lifetimes of LECs containing [Cu(xantphos)(Etbpy)][PF6] and [Cu(POP)(Etbpy)][PF6] exceed 40 and 80 h respectively

Transparent Light-Emitting Electrochemical Cells

Single layer light-emitting electrochemical cells (LECs) are amongst the simplest electroluminescent devices and operate with air-stable electrodes. Transparent light-emitting devices are of great interest as they can enable new applications in consumer electronics. In this work, a transparent ionic transition metal complex based LEC is fabricated by developing a transparent top contact based on tin (IV) oxide (SnO2) and indium-tin oxide, processed by low-temperature atomic layer deposition and pulsed laser deposition, respectively. The resulting devices present transparency in excess of 75% over the full visible spectrum (380-750 nm), with 82% transmission at the emission peak (563 nm). The devices emit from the front and the rear with high luminance (260 cd m−2) and long lifetime (176 h). These parameters place them among the highest performing single layer transparent electroluminescent devices

Increased conductivity of a hole transport layer due to oxidation by a molecular nanomagnet

Thin film transistors based on polyarylamine poly(N,N′-diphenyl-N,N′bis(4-hexylphenyl)-[1,1′biphenyl]-4,4′-diamine (pTPD) were fabricated using spin coating in order to measure the mobility of pTPD upon oxidation. Partially oxidized pTPD with a molecular magnetic cluster showed an increase in mobility of over two orders of magnitude. A transition in the mobility of pTPD upon doping could also be observed by the presence of a maximum obtained for a given oxidant ratio and subsequent decrease for a higher ratio. Such result agrees well with a previously reported model based on the combined effect of dipolar broadening of the density of states and transport manifold [email protected] [email protected]

Frontal plane pelvic motion during gait captures hip osteoarthritis related disability

Gait analysis has widely been accepted as an objective measure of function and clinical outcome. Ambulatory accelerometer-based gait analysis has emerged as a clinically more feasible alternative to optical motion capture systems but does not provide kinematic characterisation to identify disease dependent mechanisms causing walking disability. This study investigated the potential of a single inertial sensor to derive frontal plane motion of the pelvis (i.e. pelvic obliquity) and help identify hip osteoarthritis (OA) related gait alterations. Patients with advanced unilateral hip OA (n = 20) were compared to patients with advanced unilateral knee OA (n = 20) and to a healthy control group (n = 20). Kinematic characterisation of frontal plane pelvic motion during gait demonstrated decreased range of motion and increased asymmetry for hip OA patients specifically. </jats:p

Low-dimensional non-toxic A3Bi2X9 compounds synthesized by a dry mechanochemical route with tunable visible photoluminescence at room temperature

We have synthesized fifteen inorganic and hybrid organic-inorganic non-toxic A3Bi2X9 compounds (A = K+, Rb+, Cs+, CH3NH3+ and HC(NH2)2+; X = I−, Br−, Cl−) through dry mechanochemistry. We demonstrate that this synthetic method is very well suited to prepare compounds from poorly soluble precursors, allowing thus the preparation of so far unreported compounds. X-ray diffraction analysis demonstrates the high crystallinity of the so-formed ternary bismuth halides. Furthermore, we show that, through substitution of the A-cation and X-anion, the bandgap of these compounds can be tuned to absorb throughout the whole visible spectrum. As-prepared powders of Cs3Bi2Br9 and Cs3Bi2I9 without any passivating agents show room-temperature photoluminescence covering the visible spectrum from 450 nm to 800 nm, making them especially promising for white-light emission

Crystal Reorientation and Amorphization Induced by Stressing Efficient and Stable P-I-N Vacuum-Processed MAPbI3 Perovskite Solar Cells

Herein, the long‐term stability of vacuum‐deposited methylammonium lead iodide (MAPbI3) perovskite solar cells (PSCs) with power conversion efficiencies (PCEs) of around 19% is evaluated. A low‐temperature atomic layer deposition (ALD) Al2O3 coating is developed and used to protect the MAPbI3 layers and the solar cells from environmental agents. The ALD encapsulation enables the MAPbI3 to be exposed to temperatures as high as 150 °C for several hours without change in color. It also improves the thermal stability of the solar cells, which maintain 80% of the initial PCEs after aging for ≈40 and 37 days at 65 and 85 °C, respectively. However, room‐temperature operation of the solar cells under 1 sun illumination leads to a loss of 20% of their initial PCE in 230 h. Due to the very thin ALD Al2O3 encapsulation, X‐ray diffraction can be performed on the MAPbI3 films and completed solar cells before and after the different stress conditions. Surprisingly, it is found that the main effect of light soaking and thermal stress is a crystal reorientation with respect to the substrate from (002) to (202) of the perovskite layer, and that this reorientation is accelerated under illumination

Density-functional study of the evolution of the electronic structure of oligomers of thiophene:Towards a model Hamiltonian

We present density-functional and time-dependent density-functional studies of the ground, ionic, and excited states of a series of oligomers of thiophene. We show that, for the physical properties, the most relevant highest occupied and lowest unoccupied molecular orbitals develop gradually from monomer molecular orbitals into occupied and unoccupied broad bands in the large length limit. We show that band gap and ionization potentials decrease with size, as found experimentally and from empirical calculations. This gives credence to a simple tight-binding model Hamiltonian approach to these systems. We demonstrate that the length dependence of the experimental excitation spectra for both singlet and triplet excitations can be very well explained with an extended Hubbard-like Hamiltonian, with a monomer on-site Coulomb and exchange interaction and a nearest-neighbor Coulomb interaction. We also study the ground and excited-state electronic structures as functions of the torsion angle between the units in a dimer, and find almost equal stabilities for the transoid and cisoid isomers, with a transition energy barrier for isomerization of only 4.3 kcal/mol. Fluctuations in the torsion angle turn out to be very low in energy, and therefore of great importance in describing even the room-temperature properties. At a torsion angle of 90° the hopping integral is switched off for the highest occupied molecular orbital levels because of symmetry, allowing a first-principles estimate of the on-site interaction minus the next-neighbor Coulomb interaction as it enters in a Hubbard-like model Hamiltonian

Vacuum-Deposited Microcavity Perovskite Photovoltaic Devices

The interaction between semiconductor materials and electromagnetic fields resonating in microcavities or the light−matter coupling is of both fundamental and practical significance for improving the performance of various photonic technologies. The demonstration of light−matter coupling effects in the emerging perovskite-based optoelectronic devices via optical pumping and electrical readout (e.g., photovoltaics) and vice versa (e.g., lightemitting diodes), however, is still scarce. Here, we demonstrate the microcavity formation in vacuum-deposited methylammonium lead iodide (CH3NH3PbI3, MAPI) p-i-n photovoltaic devices fabricated between two reflecting silver electrodes. We tune the position of the microcavity mode across MAPI's absorption edge and study the effect on the microcavity absorption enhancement. Tuning the microcavity mode toward lower energies enhances the absorption of the lower energy photons and steepens the absorption onset which reduces the effective optical gap (Eg) of the devices. This leads to a reduction in the open circuit voltage deficit