Evaporable Fullerene Indanones with Controlled Amorphous Morphology as Electron Transport Layers for Inverted Perovskite Solar Cells.

Fullerenes are among the most commonly used electron-transporting materials (ETMs) in inverted perovskite solar cells (IPSCs). Although versatile functionalized fullerene derivatives have shown excellent performance in IPSCs, pristine [60]fullerene (C60) is still the most widely used in devices mainly because of its uniform morphology by thermal deposition. However, thermally evaporable fullerene derivatives have not yet been achieved. Herein, we developed a series of evaporable fullerene derivatives, referred to as fullerene indanones (FIDOs), affording IPSCs with high power conversion efficiency (PCE) and long-term storage stability. The FIDOs were designed with a unique architecture in which the fullerene moiety and a benzene ring moiety are linked via a five-membered carbon ring in benzene ring plane. This molecular arrangement affords exceptional thermal stability, allowing the FIDOs to withstand harsh thermal deposition conditions. Moreover, by manipulating the steric bulk of the functional groups, we could control the state of the organic film from crystalline to amorphous. Subsequently, we used FIDOs as an electron transport layer (ETL) in IPSCs. Thanks to the suitable energy level and dual-passivation effect of FIDOs compared with a reference ETL using C60, the device using FIDOs achieved an open-circuit voltage of 1.16 V and a fill factor of 0.77. As a result, the PCE reached 22.11%, which is superior to 20.45% of the best-performing reference device. Most importantly, the FIDO-based IPSC devices exhibited exceptional stability in comparison to the reference device due to the stability of the amorphous ETL films.

Synthesis of neutral Li-endohedral PCBM: an n-dopant for fullerene derivatives.

Li@PCBM, the first neutral Li@C60 derivative, was synthesized. The Li@PCBM exists in a monomer-dimer equilibrium in solution but as a monomer in the PCBM matrix. The fully dispersed Li@PCBM n-doped the surrounding empty PCBM, raising the Fermi level by 0.13 eV compared with the undoped PCBM film. The hybrid films were utilized as an ETL for PSCs, promoting the efficiency of the device.

Triarylamine/Bithiophene Copolymer with Enhanced Quinoidal Character as Hole-Transporting Material for Perovskite Solar Cells.

Polytriarylamine is a popular hole-transporting materials (HTMs) despite its suboptimal conductivity and significant recombination at the interface in a solar cell setup. Having noted insufficient conjugation among the triarylamine units along the polymer backbone, we inserted a bithiophene unit between two triarylamine units through iron-catalyzed C-H/C-H coupling of a triarylamine/thiophene monomer so that two units conjugate effectively via four quinoidal rings when the molecule functions as HTM. The obtained triarylamine/bithiophene copolymer (TABT) used as HTM showed a high-performance in methylammonium lead iodide perovskite (MAPbI3 ) solar cells. Mesityl substituted TABT forms a uniform film, shows high hole-carrier mobility, and has an ionization potential (IP=5.40 eV) matching that of MAPbI3 . We fabricated a solar cell device with a power conversion efficiency of 21.3 % and an open-circuit voltage of 1.15 V, which exceeds the performance of devices using reference standard such as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine (PTAA) and Spiro-OMeTAD.

Synthesis of Conjugated Donor-Acceptor Antiaromatic Porphyrins and Their Application to Perovskite Solar Cells.

A conjugated donor-acceptor antiaromatic porphyrin, composed of an antiaromatic thieno-fused porphyrin structure and a diketopyrrolopyrrole mioety, was synthesized and applied in a perovskite solar cell for the first time. Enhanced light absorption in the device by the antiaromatic porphyrin resulted in a significantly increased power conversion efficiency of 19.3%.

One-step direct oxidation of fullerene-fused alkoxy ethers to ketones for evaporable fullerene derivatives.

Ketones are widely applied moieties in designing functional materials and are commonly obtained by oxidation of alcohols. However, when alcohols are protected/functionalized, the direct oxidation strategies are substantially curbed. Here we show a highly efficient copper bromide promoted one-step direct oxidation of benzylic ethers to ketones with the aid of a fullerene pendant. Mechanistic studies unveil that fullerene can serve as an electron pool proceeding the one-step oxidation of alkoxy group to ketone. In the absence of the fullerene pendant, the unreachable activation energy threshold hampers the direct oxidation of the alkoxy group. In the presence of the fullerene pendant, generated fullerene radical cation can activate the neighbour C-H bond of the alkoxy moiety, allowing a favourable energy barrier for initiating the direct oxidation. The produced fullerene-fused ketone possesses high thermal stability, affording the pin-hole free and amorphous electron-transport layer with a high electron-transport mobility.

Denatured M13 Bacteriophage-Templated Perovskite Solar Cells Exhibiting High Efficiency.

The M13 bacteriophage, a nature-inspired environmentally friendly biomaterial, is used as a perovskite crystal growth template and a grain boundary passivator in perovskite solar cells. The amino groups and carboxyl groups of amino acids on the M13 bacteriophage surface function as Lewis bases, interacting with the perovskite materials. The M13 bacteriophage-added perovskite films show a larger grain size and reduced trap-sites compared with the reference perovskite films. In addition, the existence of the M13 bacteriophage induces light scattering effect, which enhances the light absorption particularly in the long-wavelength region around 825 nm. Both the passivation effect of the M13 bacteriophage coordinating to the perovskite defect sites and the light scattering effect intensify when the M13 virus-added perovskite precursor solution is heated at 90 °C prior to the film formation. Heating the solution denatures the M13 bacteriophage by breaking their inter- and intra-molecular bondings. The denatured M13 bacteriophage-added perovskite solar cells exhibit an efficiency of 20.1% while the reference devices give an efficiency of 17.8%. The great improvement in efficiency comes from all of the three photovoltaic parameters, namely short-circuit current, open-circuit voltage, and fill factor, which correspond to the perovskite grain size, trap-site passivation, and charge transport, respectively.

Successively Regioselective Electrosynthesis and Electron Transport Property of Stable Multiply Functionalized [60]Fullerene Derivatives.

With the recent advance in chemical modification of fullerenes, electrosynthesis has demonstrated increasing importance in regioselective synthesis of novel fullerene derivatives. Herein, we report successively regioselective synthesis of stable tetra- and hexafunctionalized [60]fullerene derivatives. The cycloaddition reaction of the electrochemically generated dianions from [60]fulleroindolines with phthaloyl chloride regioselectively affords 1,2,4,17-functionalized [60]fullerene derivatives with two attached ketone groups and a unique addition pattern, where the heterocycle is rearranged to a [5,6]-junction and the carbocycle is fused to an adjacent [6,6]-junction. This addition pattern is in sharp contrast with that of the previously reported biscycloadducts, where both cycles are appended to [6,6]-junctions. The obtained tetrafunctionalized compounds can be successively manipulated to 1,2,3,4,9,10-functionalized [60]fullerene derivatives with an intriguing "S"-shaped configuration via a novel electrochemical protonation. Importantly, the stability of tetrafunctionalized [60]fullerene products allows them to be applied in planar perovskite solar cells as efficient electron transport layers.

Highly Selective Synthesis of Tetrahydronaphthaleno[60]fullerenes via Fullerene-Cation-Mediated Intramolecular Cyclization.

A high-yielding protocol to construct six-membered carbon rings on fullerene is presented. This methodology with in situ fullerene-cation-mediated intramolecular cyclization provides high selectivity and efficient access to six-membered tetrahydronaphthaleno[60]fullerenes with a remarkable functional group tolerance and excellent yields. Furthermore, high solubilities of tetrahydronaphthaleno[60]fullerenes are reported.

Controlled Redox of Lithium-Ion Endohedral Fullerene for Efficient and Stable Metal Electrode-Free Perovskite Solar Cells.

High efficiency perovskite solar cells have underpinned the rapid growth of the field. However, their low device stability limits further advancement. Hygroscopic lithium bis(trifluoromethanesulfonyl)imide (Li+TFSI-) and metal electrode are the main causes of the device instability. In this work, the redox reaction between lithium-ion endohedral fullerenes and 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobi-fluorene (spiro-MeOTAD) was controlled to optimize the amount of oxidized spiro-MeOTAD and antioxidizing neutral endohedral fullerenes. Application of this mixture to metal-free carbon nanotube (CNT)-laminated perovskite solar cells resulted in 17.2% efficiency with a stability time of more than 1100 h under severe conditions (temperature = 60 °C, humidity = 70%). Such high performance is attributed to the uninhibited charge flow, no metal-ion migration, and the enhanced antioxidizing activity of the devices.

Li@C60 endohedral fullerene as a supraatomic dopant for C60 electron-transporting layers promoting the efficiency of perovskite solar cells.

C60:Li@C60 hybrid n-type semiconducting films were first fabricated. The Fermi level of 1% Li@C60-added C60 films was determined to be -4.52 eV, which was 0.12 eV higher than that of pristine C60 films. A fraction of Li@C60 is distributed uniformly within the C60 film. Its application in PSCs was demonstrated, in which the addition of Li@C60 into a C60 film improved the device performance.

Non-Solvent Fractionation of Lignin Enhances Carbon Fiber Performance.

Even though lignin carbon fiber has been sought after for several decades, the poor mechanical performance remains to be a major barrier for commercial applications. The low mechanical performance is attributed to the heterogeneity of lignin polymer. Recent advances in fractionation technologies showed the great potential to reduce lignin heterogeneity, but current fractionation methods often depend on costly chemicals and materials such as enzymes, organic solvents, membranes, and dialysis tubes. Here, a new non-solvent strategy was developed to fractionate lignin by autohydrolysis. By using only water, lignin was efficiently fractionated into water-soluble and -insoluble fractions. The latter fraction had increased molecular weight and uniformity and resulted in more ß-O-4 interunitary linkages as analyzed by size-exclusion chromatography and 2D heteronuclear single quantum coherence NMR spectroscopy, respectively. In particular, the water-insoluble fraction significantly enhanced the mechanical performances of the resultant carbon fibers. Mechanistic study by differential scanning calorimetry (DSC) revealed that the miscibility of lignin with guest polyacrylonitrile molecules was improved with the reduced lignin heterogeneity. Crystallite analyses by XRD and Raman spectroscopy revealed that the crystallite size and content of the pre-graphitic turbostratic carbon structure were increased. The fundamental understanding revealed how lignin fractionation could modify lignin chemical features to enhance the mechanical performance of resultant carbon fibers. The autohydrolysis fractionation thus represents a green, economic, and efficient methodology to process lignin waste and boost lignin carbon fiber quality, which could open new horizons for lignin valorization.

Vapor-Assisted Ex-Situ Doping of Carbon Nanotube toward Efficient and Stable Perovskite Solar Cells.

Single-walled carbon nanotubes (CNTs) has been considered as a promising material for a top electrode of perovskite solar cells owing to its hydrophobic nature, earth-abundance, and mechanical robustness. However, its poor conductivity, a shallow work function, and nonreflective nature have limited further enhancement in power conversion efficiency (PCE) of top CNT electrode-based perovskite solar cells. Here, we introduced a simple and scalable method to address these issues by utilizing an ex-situ vapor-assisted doping method. Trifluoromethanesulfonic acid (TFMS) vapor doping of the free-standing CNT sheet enabled tuning of conductivity and work function of the CNT electrode without damaging underneath layers. The sheet resistance of the CNT sheet was decreased by 21.3% with an increase in work function from 4.75 to 4.96 eV upon doping of TFMS. In addition, recently developed 2D perovskite-protected Cs-containing formamidium lead iodide (FACsPbI3) technology was employed to maximize the absorption. Because of the lowered resistance, better energy alignment, and improved absorption, the CNT electrode-based PSCs produced a PCE of 17.6% with a JSC of 24.21 mA/cm2, VOC of 1.005 V, and FF of 0.72. Furthermore, the resulting TFMS-doped CNT-PSCs demonstrated higher thermal and operational stability than bare CNT and metal electrode-based devices.

Achieving High Efficiency in Solution-Processed Perovskite Solar Cells Using C60/C70 Mixed Fullerenes.

Fullerenes have attracted considerable interest as an electron-transporting layer in perovskite solar cells. Fullerene-based perovskite solar cells produce no hysteresis and do not require high-temperature annealing. However, high power conversion efficiency has been only achieved when the fullerene layer is thermally evaporated, which is an expensive process. In this work, the limitations of a solution-processed fullerene layer have been identified as high crystallinity and the presence of remnant solvents, in contrast to a thermally deposited C60 film, which has low crystallinity and no remaining solvents. As a solution to these problems, a mixed C60 and C70 solution-processed film, which exhibits low crystallinity, is proposed as an electron-transporting layer. The mixed-fullerene-based devices produce power conversion efficiencies as high as that of the thermally evaporated C60-based device (16.7%) owing to improved fill factor and open-circuit voltage. In addition, by vacuum-drying the mixed fullerene film, the power conversion efficiency of the solution-processed perovskite solar cells is further improved to 18.0%. This improvement originates from the enhanced transmittance and charge transport by removing the solvent effect. This simple and low-cost method can be easily used in any type of solar cells with fullerene as the electron-transporting layer.

Functionalization of [60]fullerene through fullerene cation intermediates.

Fullerene cations, namely [60]fullerene radical cation (C60˙+) and organo[60]fullerenyl cation (RC60+), are less investigated as intermediates in synthetic fullerene chemistry because of the intrinsic electronegativity of C60. Remarkably, these two intermediates can mediate reactions that afford versatile, unique and unexpected fullerene derivatives. This review article mainly describes these C60˙+ and RC60+ intermediates and includes a variety of topics, from the generation of C60˙+ and RC60+ species to their applications in fullerene modification reactions, such as Friedel-Crafts hydroarylation, nucleophilic addition, dimerization, intramolecular rearrangement reactions, and intramolecular cyclization reactions. Additionally, this review deeply discusses the mechanism of the formation of unique [60]fullerene derivatives involving [60]fullerene radical cation and organo[60]fullerenyl cation intermediates. In addition, the electrochemical properties and photovoltaic performance of these fullerene derivatives produced through C60˙+ or RC60+-mediated reactions are discussed in this review.

Fullerene-Cation-Mediated Noble-Metal-Free Direct Introduction of Functionalized Aryl Groups onto [60]Fullerene.

Aryl[60]fullerenyl cations (ArC60+), which were generated by heating aryl[60]fullerenyl dimers (ArC60-C60Ar) to generate aryl[60]fullerenyl radicals (ArC60•) followed by oxidation using Cu(II) salts (Cu(BF4)2(aq)), were reacted with various functionalized aryl boronic acids to produce functionalized 1,4-diaryl[60]fullerenes. This protocol tolerated various functional groups, such as OH, NH2, COCH3, and Cl substituents, with yields reaching 93%. C60Ar1Ar2 (Ar2 = p-NH2C6H4) was used as a dopant in a photoactive CH3NH3PbI3 layer of a perovskite solar cell.

Solvent-free iodine-promoted synthesis of 3,2'-pyrrolinyl spirooxindoles from alkylidene oxindoles and enamino esters under ball-milling conditions.

A novel solvent-free iodine-promoted cyclization of alkylidene oxindoles with enamino esters via C-C/C-N bond formation has been demonstrated under ball-milling conditions. This protocol provides efficient and green access to a variety of 3,2'-pyrrolinyl spirooxindoles with remarkable functional group tolerance, good yields and excellent diastereoselectivities.

Palladium-Catalyzed Decarboxylative ortho-Acylation of Benzamides with α-Oxocarboxylic Acids.

A palladium-catalyzed decarboxylative ortho-acylation of tertiary benzamides with α-oxocarboxylic acids by weak O-coordination has been described. This reaction proceeds smoothly with a high monoacylation selectivity, affording ortho-acylated benzamides in moderate to good yields. When secondary benzamides are employed as the substrates, the formed ortho-acylated benzamides undergo further intramolecular cyclization to provide isoindolinone derivatives. In addition, several transformations of the synthesized ortho-acylated benzamides into a diversity of synthetically valuable products have been demonstrated.

The cyclopropanation of [60]fullerobenzofurans via electrosynthesis.

The electrochemical cyclopropanation of [60]fullerobenzofurans with diethyl dibromomalonate has been investigated. Controlled by the steric effect, the sterically favored e bisadducts are obtained as the major products along with two trans-3 bisadducts as minor products. The addition sites and patterns of this reaction are very different from those of our previously reported reaction with benzyl bromide, providing insights into the controlling factors for the electrophilic reactions of dianionic fullerene derivatives.

Effect of fermented soy milk on the intestinal bacterial ecosystem.

AIM: To investigate the effect of fermented soy milk on human ecosystem in the intestinal tract by way of examining the population of different microorganisms isolated from fecal samples. METHODS: A crossover experimental design was applied. Twenty-eight healthy adults completed this experiment. Each subject consumed 250 mL, twice a day between meals, of either fermented soy milk or regular soy milk first for 2 wk, then switched to the other drink after 2 wk. Fecal samples were collected from all subjects every week starting from the second week to the end of the experiment. The microorganisms analyzed were Bifidobacterium spp., Lactobacillus spp., Clostridium perfringens, coliform organisms, and total anaerobic organisms. RESULTS: In the period of fermented soy milk consumption, the populations of Bifidobacterium spp. and Lactobacillus spp. increased (P<0.05) as well as the ratios of Bifidobacterium spp. and Lactobacillus spp. to Clostridium perfringens (P<0.05). The population of coliform organisms decreased (P<0.05) when subjects were in the period of fermented soy milk consumption. CONCLUSION: Intake of fermented soy milk significantly improved the ecosystem of the intestinal tract in the body by increasing the amount of probiotics.