In-Situ Cyclized Polyacrylonitrile as an Electron Selective Layer for n-i-p Perovskite Solar Cell with Enhanced Efficiency and Stability.

In situ cyclized polyacrylonitrile (CPAN) is developed to replace n-type metal oxide semiconductors (TiO2 or SnO2) as an electron selective layer (ESL) for highly efficient and stable n-i-p perovskite solar cells (PSCs). The CPAN layer is fabricated via facile in situ cyclization reaction of polyacrylonitrile (PAN) coated on a conducting glass substrate. The CPAN layer is robust and insoluble in common solvents, and possesses n-type semiconductor properties with a high electron mobility of 4.13×10-3 cm2 V-1 s-1. With the CPAN as an ESL, the PSC affords a power conversion efficiency (PCE) of 23.12 %, which is the highest for the n-i-p PSCs with organic ESLs. Moreover, the device with the CPAN layer holds superior operational stability, maintaining over 90 % of their initial efficiency after 500 h continuous light soaking. These results confirm that the CPAN layer would be a desirable low-cost and efficient ESL for n-i-p PSCs and other photoelectronic devices with high performance and stability.

A Cation-Exchange Approach for the Fabrication of Efficient Methylammonium Tin Iodide Perovskite Solar Cells.

Tin-based halide perovskite materials have been successfully employed in lead-free perovskite solar cells, but the overall power conversion efficiencies (PCEs) have been limited by the high carrier concentration from the facile oxidation of Sn2+ to Sn4+ . Now a chemical route is developed for fabrication of high-quality methylammonium tin iodide perovskite (MASnI3 ) films: hydrazinium tin iodide (HASnI3 ) perovskite film is first solution-deposited using presursors hydrazinium iodide (HAI) and tin iodide (SnI2 ), and then transformed into MASnI3 via a cation displacement approach. With the two-step process, a dense and uniform MASnI3 film is obtained with large grain sizes and high crystallization. Detrimental oxidation is suppressed by the hydrazine released from the film during the transformation. With the MASnI3 as light harvester, mesoporous perovskite solar cells were prepared, and a maximum power conversion efficiency (PCE) of 7.13 % is delivered with good reproducibility.

Nickel-catalyzed triarylamine synthesis: synthetic and mechanistic aspects.

An improved protocol was described for the amination of chloroarenes with diarylamines under NiCl2(PCy3)2 catalysis in the presence of a Grignard reagent as base. This method fully suits bromo-/iodoarene substrates as well, and even is expanded to certain aryl tosylates. A preliminary investigation into the mechanism suggests that this amination reaction might proceed through Ni(I) and Ni(III) intermediates rather than via the usually expected Ni(0)-Ni(II) cycle.

Electrochemical assembly of single-walled carbon nanotube/polypyrrole/tellurium/lead telluride multi-layer nanocomposite films for room-temperature flexible thermoelectric application.

With the complexity and diversification of thermoelectric (TE) application scenarios, it becomes increasingly difficult for single-component thermoelectric materials to satisfy practical demands. Therefore, recent researches have largely focused on the development of the multi-component nanocomposites, which are probably a good solution for the TE application of some materials that are not eligible when used alone. In this work, a seires of single-walled carbon nanotube (SWCNT)/polypyrrole (PPy)/tellurium (Te)/lead telluride (PbTe) multi-layer flexible composite films were fabricated via the successive electrodeposition of the flexible PPy layer with a low thermal conductivity, the ultra-thin Te induction layer, and the brittle PbTe layer with a large Seebeck coefficient over the pre-fabricated SWCNT membrane electrode with a high electrical conductivity. Through the complementary advantages between different components and the multiple synergies of the interface engineering, the SWCNT/PPy/Te/PbTe composites harvested the excellent TE performance with a maximum power factor (PF) of 929.8 ± 35.4 µW m-1 K-2 at room temperature, outperforming those of most of the electrochemically-prepared organic/inorganic TE composites reported previously. This work evidenced that the electrochemical multi-layer assembly is a feasible tactic for constructing special thermoelectric materials to meet customized requirements, which could also be applied to other material platforms.

Full-Electrochemical Construction of High-Performance Polypyrrole/Tellurium Thermoelectrical Nanocomposites.

As one of the most attractive inorganics to improve the thermoelectric (TE) performance of the conducting polymers, tellurium (Te) has received intense concern due to its superior Seebeck coefficient (S). However, far less attention has been paid to polypyrrole (PPy)/Te TE composites to date. In this work, we present an innovative full-electrochemical method to architect PPy/Te TE composite films by sequentially depositing Te with large S and PPy with high electrical conductivity (σ). Consequently, the PPy/Te composite films achieved excellent TE performance, with the largest power factor (PF) reaching up to 234.3 ± 4.1 µW m-1 K-2. To the best of our knowledge, this value approaches the reported highest PF record (240.3 ± 5.0 µW m-1 K-2) for PPy-based composites. This suggests that the modified full-electrochemical method is a feasible and effective strategy for achieving high-performance TE composite films, which would probably provide a general guideline for the design and preparation of excellent TE materials in the future.

Pseudo in situ construction of high-performance thermoelectric composites with a dioxothiopyrone-based D-A polymer coating on SWCNTs.

Organic polymer/inorganic particle composites with thermoelectric (TE) properties have witnessed rapid progress in recent years. Nevertheless, both development of novel polymers and optimization of compositing methods remain highly desirable. In this study, we first demonstrated a simulated in situ coagulation strategy for construction of high-performance thermoelectric materials by utilizing single-walled carbon nanotubes (SWCNTs) and a new D-A polymer TPO-TTP12 that was synthesized via incorporating dioxothiopyrone subunit into a polymeric chain. It was proven that the preparation methods have a significant influence on thermoelectric properties of the TPO-TTP12/SWCNT composites. The in situ prepared composite films tend to achieve much better thermoelectric performances than those prepared by simply mixing the corresponding polymer with SWCNTs. As a result, the in situ compositing obtains the highest Seebeck coefficient of 66.10 ± 0.05 µV K-1 at the TPO-TTP12-to-SWCNT mass ratio of 1/2, and the best electrical conductivity of up to 500.5 ± 53.3 S cm-1 at the polymer/SWCNT mass ratio of 1/20, respectively; moreover, the power factor for the in situ prepared composites reaches a maximum value of 141.94 ± 1.47 µW m-1 K-2, far higher than that of 104.68 ± 0.86 µW m-1 K-2 for the by-mixing produced composites. This indicates that the dioxothiopyrone moiety is a promising building block for constructing thermoelectric polymers, and the simulated in situ compositing strategy is a promising way to improve TE properties of composite materials.

Facile Modification of a Noncovalently Fused-Ring Electron Acceptor Enables Efficient Organic Solar Cells.

Electron acceptors with nonfused aromatic cores (NCAs) have aroused increasing interest in organic solar cells due to the low synthetic complexity and flexible chemical modification, but the corresponding device performance still lags behind. Herein, we designed and synthesized two new quinoxaline-based NCAs, namely, QOC6-4H and QOC6-4Cl. Although both NCAs show good backbone coplanarity, QOC6-4Cl with chlorinated end groups exhibits higher extinction coefficient, enhanced crystallinity, and more compact π-π stacking, which is correlated with the stronger intermolecular interactions induced by chlorine atoms. Benefiting from the broader and stronger optical absorption, improved carrier mobilities, and suppressed charge recombination, a notable power conversion efficiency (PCE) of 12.32% with a distinctly higher short-current density (Jsc) of 22.91 mA cm-2 and a fill factor (FF) of 69.01% could be obtained for the PBDB-T:QOC6-4Cl-based device. The PCEs of PBDB-T:QOC6-4H were only lower than 8%, which could mainly be attributed to the unsymmetric charge transport. Our work proves that the chlorination of end groups is a facile and effective strategy to enhance the intermolecular interactions and thus the photovoltaic performance of NCAs, and a careful modulation of the intermolecular interactions plays a vital role in further developing both high-performance and low-cost organic photovoltaic materials.

Organic-inorganic hybrid perovskite for low-cost and high-performance xerographic photoreceptors.

Solution-processable organic-inorganic hybrid perovskites are being widely investigated for many applications, including solar cells, light-emitting diodes, photodetectors, and lasers. Herein, we report, for the first time, successful fabrication of xerographic photoreceptors using methylammonium lead iodide (CH3NH3PbI3) perovskite as a light-absorbing material. With the incorporation of polyethylene glycol (PEG) into the perovskite film, the ion migration inherent to the perovskite material can be effectively suppressed, and the resulting photoreceptor exhibits a high and panchromatic photosensitivity, large surface potential, low dark decay, and high environmental resistance and electrical cycling stability. Specifically, the energies required to photodischarge one half of the initial surface potential (E 0.5) are 0.074 µJ cm-2 at 550 nm and 0.14 µJ cm-2 at 780 nm, respectively. The photosensitivites outmatch those of the conventionally used organic pigments having narrow spectral responses. Our findings inform a new generation of highly efficient and low-cost xerographic photoreceptors based on perovskite materials.

Methylamine-assisted growth of uniaxial-oriented perovskite thin films with millimeter-sized grains.

Defects from grain interiors and boundaries of perovskite films cause significant nonradiative recombination energy loss, and thus perovskite films with controlled crystallinity and large grains is critical for improvement of both photovoltaic performance and stability for perovskite-based solar cells. Here, a methylamine (MA0) gas-assisted crystallization method is developed for fabrication of methylammonium lead iodide (MAPbI3) perovskite films. In the process, the perovskite film is formed via controlled release of MA0 gas molecules from a liquid intermediate phase MAPbI3·xMA0. The resulting perovskite film comprises millimeter-sized grains with (110)-uniaxial crystallographic orientation, exhibiting much low trap density, long carrier lifetime, and excellent environmental stability. The corresponding perovskite solar cell exhibits a power conversion efficiency (PCE) of ~ 21.36%, which is among the highest reported for MAPbI3-based devices. This method provides important progress towards the fabrication of high-quality perovskite thin films for low-cost, highly efficient and stable perovskite solar cells.

Ion Exchange/Insertion Reactions for Fabrication of Efficient Methylammonium Tin Iodide Perovskite Solar Cells.

The low toxicity, narrow bandgaps, and high charge-carrier mobilities make tin perovskites the most promising light absorbers for low-cost perovskite solar cells (PSCs). However, the development of the Sn-based PSCs is seriously hampered by the critical issues of poor stability and low power conversion efficiency (PCE) due to the facile oxidation of Sn2+ to Sn4+ and poor film formability of the perovskite films. Herein, a synthetic strategy is developed for the fabrication of methylammonium tin iodide (MASnI3) film via ion exchange/insertion reactions between solid-state SnF2 and gaseous methylammonium iodide. In this way, the nucleation and crystallization of MASnI3 can be well controlled, and a highly uniform pinhole-free MASnI3 perovskite film is obtained. More importantly, the detrimental oxidation can be effectively suppressed in the resulting MASnI3 film due to the presence of a large amount of remaining SnF2. This high-quality perovskite film enables the realization of a PCE of 7.78%, which is among the highest values reported for the MASnI3-based solar cells. Moreover, the MASnI3 solar cells exhibit high reproducibility and good stability. This method provides new opportunities for the fabrication of low-cost and lead-free tin-based halide perovskite solar cells.

Novel TPD-based organic D-pi-A dyes for dye-sensitized solar cells.

A novel class of organic D-pi-A dyes employing a N,N,N',N'-tetraphenylbenzidine (TPD) unit as donor was designed and synthesized for dye-sensitized solar cells, which achieved a solar-to-electricity conversion efficiency (eta) of 5.63% in preliminary tests as compared to 6.42% for N3 dye under the same experimental conditions.

Nickel-catalyzed cross-coupling of diarylamines with haloarenes.

The cross-coupling reaction of diarylamines with aryl bromides/iodides can be effected by the Ni(ii)-(sigma-aryl) complex/PPh(3)/NaH system, and a preliminary investigation was conducted into the mechanism of this reaction.

t-BuOK-catalysed alkylation of fluorene with alcohols: a highly green route to 9-monoalkylfluorene derivatives.

A simple, mild and efficient protocol was developed for the alkylation of fluorene with alcohols in the presence of t-BuOK as catalyst, affording the desired 9-monoalkylfluorenes with near quantitative yields in most cases.

trans-(4-Acetyl-naphth-yl)chlorido-bis(triphenyl-phosphine-κP)nickel(II) dichloro-methane solvate.

The title compound, [Ni(C(12)H(9)O)Cl(C(18)H(15)P)(2)]·CH(2)Cl(2), was synthesized from the reaction between 1-acetyl-4-chloro-naphthalene, NiCl(2)·6H(2)O and triphenyl-phosphine (PPh(3)) in ethanol. The compound contains one crystallographically unique nickel ion in a pseudo-square-planar geometry.

A Novel Strategy for Scalable High-Efficiency Planar Perovskite Solar Cells with New Precursors and Cation Displacement Approach.

Methylammonium iodide (MAI) and lead iodide (PbI2 ) have been extensively employed as precursors for solution-processed MAPbI3 perovskite solar cells (PSCs). However, the MAPbI3 perovskite films directly deposited from the precursor solutions, usually suffer from poor surface coverage due to uncontrolled nucleation and crystal growth of the perovskite during the film formation, resulting in low photovoltaic conversion efficiency and poor reproducibility. Herein, propylammonium iodide and PbI2 are employed as precursors for solution deposition of propylammonium lead iodide (PAPbI3 ) perovskite film. It is found that the precursors have good film formability, enabling the deposition of a large-area and homogeneous PAPbI3 perovskite film by a scalable dip-coating technique. The dip-coated PAPbI3 film is then subjected to an organic-cation displacement reaction, resulting in MAPbI3 film with high surface coverage and crystallinity. With the MAPbI3 film as the light absorber, planar PSCs are fabricated, and stabilized power conversion efficiencies of 19.27% and 15.68% can be achieved for the devices with active areas of 0.09 and 5.02 cm2 , respectively. The technology reported here provides a robust and efficient approach to fabricate large-area and high-efficiency perovskite cells for practical application.

Novel organic dyes for efficient dye-sensitized solar cells.

Two novel metal-free organic dyes containing thienothiophene and thiophene segments have been synthesized. Nano-crystalline TiO2 dye-sensitized solar cells were fabricated using these dyes as light-harvesting sensitizers, and a high solar energy-to-electricity conversion efficiency of 6.23% was achieved.

Arylation of diarylamines catalyzed by Ni(II)-PPh3 system.

[reaction: see text]. The cross-coupling of bromomagnesium diarylamides, generated in situ from diarylamines, with aryl bromides or iodides can be effected with a simple NiCl2(PPh3)2-PPh3 catalyst system under relatively mild conditions. This coupling reaction is an inexpensive, convenient, and practical method, functioning as an alternative to the corresponding Pd-catalyzed or Cu-mediated process for the synthesis of triarylamines.

Direct Conversion of CH3NH3PbI3 from Electrodeposited PbO for Highly Efficient Planar Perovskite Solar Cells.

Organic-inorganic hybrid perovskite materials have recently been identified as a promising light absorber for solar cells. In the efficient solar cells, the perovskite active layer has generally been fabricated by either vapor deposition or two-step sequential deposition process. Herein, electrochemically deposited PbO film is in situ converted into CH3NH3PbI3 through solid-state reaction with adjacent CH3NH3I layer, exhibiting a large-scale flat and uniform thin film with fully substrate coverage. The resultant planar heterojunction photovoltaic device yields a best power conversion efficiency of 14.59% and an average power conversion efficiency of 13.12 ± 1.08% under standard AM 1.5 conditions. This technique affords a facile and environment-friendly method for the fabrication of the perovskite based solar cells with high reproducibility, paving the way for the practical application.

Kumada-Corriu reactions of alkyl halides with alkynyl nucleophiles.

[reaction: see text] Pd(2)(dba)(3)-Ph(3)P-catalyzed Kumada-Corriu coupling reactions of unactivated alkyl bromides or iodides with an alkynyl nucleophile furnish C(sp)-C(sp)3 bond formation. Alkynyl nucleophiles can be alkynyllithiums or the corresponding Grignard reagents. The superior performance of Ph(3)P ligand over the trialkylphosphine ligands indicates that this cross-coupling reaction may be a reductive-elimination-controlled process.