VOC Over 1.4 V for Amorphous Tin-Oxide-Based Dopant-Free CsPbI2Br Perovskite Solar Cells.

CsPbI2Br perovskite solar cells have attracted much attention because of the rapid development in their efficiency and their great potential as a top cell of tandem solar cells. However, the VOC outputs observed so far in most cases are far from that desired for a top cell. Up to now, with various kinds of treatments, the reported champion VOC is only 1.32 V, with a VOC deficit of 0.60 V. In this work, we found that aging of the SnCl2 precursor solution for the electron-transporting layer can promote the VOC of CsPbI2Br solar cells by employing a dopant-free-polymer hole transport material (HTM) over 1.40 V and efficiency over 15.5% with high reproducibility. With the champion VOC of 1.43 V, the VOC deficit was reduced to <0.50 V, which is achieved for the first time. This simple technique of SnCl2 solution aging forms a uniform and smooth amorphous SnOx film with pure Sn4+, elevates the conduction band of SnOx, and reduces the interfacial gaps and the trap state density of the device, resulting in enhancement in average VOC from ∼1.2 V in the nonaged case to ∼1.4 V in the aged case. Furthermore, the device using an aged SnCl2 solution also exhibits a much better long-term stability than that made of the fresh solution. These achievements in dopant/additive-free CsPbI2Br solar cells can be useful for future research on CsPbI2Br and tandem solar cells.

Organic/Inorganic Hybrid p-Type Semiconductor Doping Affords Hole Transporting Layer Free Thin-Film Perovskite Solar Cells with High Stability.

A feature of perovskite devices is their suitability in the fabrication of semitransparent solar cells (ST-SCs). Methylammonium lead iodide based perovskite material (MAPbI3 or PV) is a possible material of choice because of its semitransparent nature in thin film form and after considering a balance among average visible light transmittance (AVT), power conversion efficiency (PCE), and device stability. However, there are issues to be addressed in the design of PV ST-SCs, such as the stability of small grain crystals forming in thin films and reducing the number of layers in the device to increase AVT. We report herein that doping PV with a 0.03 wt % hybrid organic p-type semiconductor, fluorinated tetraarylbenzo [1,2- b:4,5- b']dipyrrol-1,5-yl alkanediylsulfonate salt (BDPSO), affords a device with a 280 nm active layer directly fabricated on an indium tin oxide/glass substrate, without fabricating a hole transporting layer. Such a device exhibited a 30% higher PCE of 16.9% than the device made without doping. This device exhibited a stable photocurrent output at the maximum power point (MPP) for >1000 s under air and an operational stability of retaining 93% of the initial PCE after 1000 h continuous light soaking at the MPP. The ST-SC devices made of BDPSO-doped 140 nm and 90 nm thick PV films and a 6 nm thick Au electrode achieved PCEs of 10.3 and 8.0% and whole device semitransparency values of 22 and 30% AVT, respectively. The origins of the observed doping effect of BDPSO are ascribed to the bissulfonate structure that can effectively passivate defects at the interface and grain boundaries and to the HOMO level matching with PV to facilitate charge transfer.

Disodium Benzodipyrrole Sulfonate as Neutral Hole-Transporting Materials for Perovskite Solar Cells.

Hole-transporting material (HTM) is an indispensable constituent in organic electronic devices, generally comprising a donor/dopant combination. We report that a disodium salt of substituted benzo[1,2- b:4,5- b']dipyrrole bearing two racemic alkanediylsulfonate anion side chains (BDPSOs) serves as a neutral, nonhygroscopic, dopant-free HTM for lead perovskite (MAPbI3) solar cells. These organic/inorganic hybrid molecules are useful for tunable orbital level and controllable solubility. A fluorinated BDPSO has an energy level matched with MAPbI3, affording an inverted-structure solar cell that performs with 17.2% efficiency with minimal hysteresis. The solar cell devices fabricated using BDPSOs showed remarkable storage and operational stability.

Synthesis and reactivity of a bis(disulfide)-bridged RuMo3S4 double-cubane cluster: a new family of nona- or decanuclear mixed-metal sulfide clusters with two RuMo3S4 units.

A bis(disulfide)-bridged RuMo3S4 double-cubane cluster [{(Cp*Mo)3(mu3-S)4Ru}(mu2-eta2:eta1-S2)]2[PF6]2 (2, Cp* = eta5-C5Me5) is readily available from cluster [(Cp*Mo)3(mu3-S)4RuH2(PPh3)][PF6] (1) and S8. The reactions of cluster 2 with [M(PPh3)4] (M = Pd, Pt) give rise to the formation of a new family of nona- or decanuclear mixed-metal sulfide clusters, [{(Cp*Mo)3(mu3-S)4Ru}2(mu3-S)2{Pd(S)(PPh3)}][PF6]2 (3), [{(Cp*Mo)3(mu3-S)4Ru}2(mu3-S)2{(Pd(PPh3))2(mu2-S)}][PF6]2 (4), and [{(Cp*Mo)3(mu3-S)4Ru}2(mu3-S)2{Pt(PPh3)2}][PF6]2 (5), with two RuMo3S4 cubane units, the structures of which have been determined by X-ray diffraction studies.

Syntheses and structures of mono-, di- and tetranuclear rhodium or iridium complexes of thiacalix[4]arene derivatives.

The reactions of [Cp*MCl2]2(Cp*=eta5-C5Me5, M = Rh, Ir) with thiacalix[4]arene (TC4A(OH)4) and tetramercaptothiacalix[4]arene (TC4A(SH)4) gave the mononuclear complexes [(Cp*M){eta3-TC4A(OH)2(O)2}] and the dinuclear complexes [(Cp*M)2{eta3eta3-TC4A(S)4}] respectively, while the analogous reactions with dimercaptothiacalix[4]arene (TC4A(OH)2(SH)2) produced the tetranuclear complexes [(Cp*M)2(Cp*MCl2)2-{eta3eta3eta1eta1-TC4A(O)2(S)2}].

Cleavage of hydrazine N-N bonds by RuMo3S4 cubane-type clusters.

The mixed-metal cubane-type clusters [(Cp*Mo)3(mu3-S)4RuH2(PR3)][PF(6)] [Cp* = eta5-C5Me5; R = Ph (2), Cy (5)] were effective for the N-N bond cleavage of hydrazine and phenylhydrazine via a disproportionation reaction. The ammonia cluster [(C*Mo)3(mu3-S)4Ru(NH3)(PPh3)][PF6] (3) and/or the unprecedented double-cubane-type cluster with bridging nitrogenous ligands [{(Cp*Mo)3(mu3-S)4Ru}2(mu2-NH2)(mu2-NHNH2)][PF6]2 (4) were isolated from the reaction mixtures, and their structures were determined by X-ray diffraction studies.