Synthesis and cycloaddition reactions of derivatives of strained alkynes derived from 2,2’-dihydroxy-1,1’-biaryls

A series of strained alkynes, based on the 2,2’-dihydroxy-1,1’-biaryl structure, were prepared in a short sequence from readily-available starting materials. These compounds can be readily converted into further derivatives including examples containing fluorescent groups with potential for use as labelling reagents. The alkynes are able to react in cycloadditions with a range of azides without the requirement for a copper catalyst, in clean reactions with no observable side reactions

Degradation of inverted architecture CH3NH3PbI3-xClx perovskite solar cells due to trapped moisture

We explore degradation pathways within encapsulated CH3NH3PbI3-xClx perovskite devices based on the inverted architecture: ITO/PEDOT:PSS/CH3NH3PbI3-xClx/PC70BM/LiF/Al. Devices were subjected to more than 670 h of continuous illumination approximating AM1.5, with a Ts80 lifetime of (280 ± 20) hours determined. Devices stored in the dark underwent a similar drop in efficiency over the same time-period. Using external quantum efficiency, time-resolved photoluminescence, X-ray diffraction, scanning electron microscopy and laser beam induced current mapping, we attribute the primary cause of degradation to reactions with residual moisture trapped in the device, resulting in the decomposition of the perovskite

Ionic Reactivity at Contacts and Aging of Methylammonium Lead Triiodide Perovskite Solar Cells

Hybrid lead halide perovskites have reached very large solar to electricity power conversion efficiencies, in some cases exceeding 20%. The most extensively used perovskite-based solar cell configuration comprises CH3NH3PbI3 (MAPbI3) in combination with electron (TiO2) and hole 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spiro-bifluorene (spiro-OMeTAD) selective contacts. The recognition that the solar cell performance is heavily affected by time scale of the measurement and preconditioning procedures has raised many concerns about the stability of the device and reliability for long-time operation. Mechanisms at contacts originate observable current–voltage distortions. Two types of reactivity sources have been identified here: (i) weak Ti–I–Pb bonds that facilitate interfacial accommodation of moving iodine ions. This interaction produces a highly reversible capacitive current originated at the TiO2/MAPbI3 interface, and it does not alter steady-state photovoltaic features. (ii) An irreversible redox peak only observable after positive poling at slow scan rates. It corresponds to the chemical reaction between spiro-OMeTAD+ and migrating I− which progressively reduces the hole transporting material conductivity and deteriorates solar cell performance.Funded by Ministerio de Economía y Competitividad. Grant Number: MAT2013-47192-C3-1-R and Generalitat Valenciana. Grant Numbers: Prometeo/2014/020, ACOMP/2015/105

Optoelectronic Studies of Methylammonium Lead Iodide Perovskite Solar Cells with Mesoporous TiO2: Separation of Electronic and Chemical Charge Storage, Understanding Two Recombination Lifetimes, and the Evolution of Band Offsets during J-V Hysteresis

Methylammonium lead iodide (MAPI) cells of the design FTO/sTiO2/ mpTiO2/MAPI/Spiro-OMeTAD/Au, where FTO is fluorine-doped tin oxide, sTiO2 indicates solid-TiO2, and mpTiO2 is mesoporous TiO2, are studied using transient photovoltage (TPV), differential capacitance, charge extraction, current interrupt, and chronophotoamperometry. We show that in mpTiO2/MAPI cells there are two kinds of extractable charge stored under operation: a capacitive electronic charge (&sim;0.2 &mu;C/ cm2) and another, larger charge (40 &mu;C/cm2), possibly related to mobile ions. Transient photovoltage decays are strongly double exponential with two time constants that differ by a factor of &sim;5, independent of bias light intensity. The fast decay (&sim;1 &mu;s at 1 sun) is assigned to the predominant charge recombination pathway in the cell. We examine and reject the possibility that the fast decay is due to ferroelectric relaxation or to the bulk photovoltaic effect. Like many MAPI solar cells, the studied cells show significant J&minus;V hysteresis. Capacitance vs open circuit voltage (Voc) data indicate that the hysteresis involves a change in internal potential gradients, likely a shift in band offset at the TiO2/MAPI interface. The TPV results show that the Voc hysteresis is not due to a change in recombination rate constant. Calculation of recombination flux at Voc suggests that the hysteresis is also not due to an increase in charge separation efficiency and that charge generation is not a function of applied bias. We also show that the J&minus;V hysteresis is not a light driven effect but is caused by exposure to electrical bias, light or dark.</div

Grain rotation and lattice deformation during perovskite spray coating and annealing probed in situ by GI-WAXS

We report for the first time on grain rotation in CH3NH3PbI3 perovskite films for ∼12% efficient planar solar cells and present a new method for investigating their texture evolution during thermal annealing. Our technique is based on in situ 2D grazing incidence wide-angle X-ray scattering (GI-WAXS) and employs a 10 keV wide-focussed X-ray beam to simultaneously probe a large number of grains. The ability to track the texture dynamics from a statistically relevant number of spots diffracting from single grains during thermal annealing and in grazing incidence geometry can have applications understanding the processing dynamics of a range of new materials

Organic gelators as growth control agents for stable and reproducible hybrid perovskite-based solar cells

Low molecular-weight organic gelators are widely used to influence the solidification of polymers, with applications ranging from packaging items, food containers to organic electronic devices, including organic photovoltaics. Here, this concept is extended to hybrid halide perovskite-based materials. In-situ time-resolved grazing incidence wide angle x-ray scattering (GIWAXS) measurements performed during spin-coating reveal that organic gelators beneficially influence the nucleation and growth of the perovskite precursor phase. This can be exploited for the fabrication of planar n-i-p heterojunction devices with MAPbI3 (MA = CH3NH3 +) that display a performance that not only is enhanced by ~25% compared to solar cells where the active layer was produced without the use of a gelator but that also feature a higher stability to moisture and a reduced hysteresis. Most importantly, the presented approach is straight-forward and simple, and it provides a general method to render the film-formation of hybrid perovskites more reliable and robust, analogous to the control that is afforded by these additives in the processing of commodity ‘plastics’

Enhancement of the Performance of Perovskite Solar Cells, LEDs, and Optical Amplifiers by Anti-Solvent Additive Deposition

The efficiency of perovskite optoelectronic devices is increased by a novel method; its suitability for perovskite solar cells, light-emitting diodes, and optical amplifiers is demonstrated. The method is based on the introduction of organic additives during the anti-solvent step in the perovskite thin-film deposition process. Additives passivate grain boundaries reducing non-radiative recombination. The method can be easily extended to other additives

Characterization and pedogenic classification of the soils of the Central Agricultural Research Station, Afgoi, Somali Democratic Republic

Thesis (M.S.)--Michigan State University. Department of Crop and Soil Sciences, 1979Includes bibliographical references (pages 66-67