Template-Mediated Control over Polymorphism in the Vapor-Assisted Formation of Zeolitic Imidazolate Framework Powders and Films.

The landscape of possible polymorphs for some metal-organic frameworks (MOFs) can pose a challenge for controlling the outcome of their syntheses. Demonstrated here is the use of a template to control in the vapor-assisted formation of zeolitic imidazolate framework (ZIF) powders and thin films. Introducing a small amount of either ethanol or dimethylformamide vapor during the reaction between ZnO and 4,5-dichloroimidazole vapor results in the formation of the porous ZIF-71 phase, whereas other conditions lead to the formation of the dense ZIF-72 phase or amorphous materials. Time-resolved in situ small-angle X-ray scattering reveals that the porous phase is metastable and can be transformed into its dense polymorph. This transformation is avoided through the introduction of template vapor. The porosity of the resulting ZIF powders and films was studied by N2 and Kr physisorption, as well as positron annihilation lifetime spectroscopy. The templating principle was demonstrated for other members of the ZIF family as well, including the ZIF-7 series, ZIF-8_Cl, and ZIF-8_Br.

Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks.

Metal-organic frameworks (MOFs) offer disruptive potential in micro- and optoelectronics because of the unique properties of these microporous materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturized solid-state devices. Conventional MOF patterning methods suffer from low resolution and poorly defined pattern edges. Here, we demonstrate the resist-free, direct X-ray and electron-beam lithography of MOFs. This process avoids etching damage and contamination and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting high-quality patterns have excellent sub-50-nm resolution, and approach the mesopore regime. The compatibility of X-ray and electron-beam lithography with existing micro- and nanofabrication processes will facilitate the integration of MOFs in miniaturized devices.

Fluorination Induced Donor to Acceptor Transformation in A1-D-A2-D-A1-Type Photovoltaic Small Molecules.

With the development of diversity of non-fullerene acceptors, it is found that there is no clear boundary between electron donors and electron acceptors. Modulation of the electron donating and withdrawing properties of organic semiconductors is necessary for organic photovoltaics research. In this work, we designed and synthesized three A1-D-A2-D-A1-type (A represents acceptor unit and D represents donor unit) small molecules, named as M-0F, M-1F, and M-2F, respectively containing zero, one, and two fluorine atoms in the terminal acceptor segments (A1), respectively. Fluorination substitution was found to be able to downshift the HOMO and LUMO energy level, red-shift the absorption, and enhance the electron mobility. The M-0F exhibited the highest efficiency of 5.99% as a donor in fullerene-containing system and the lowest efficiency of 0.58% as an acceptor in fullerene-free system. While the M-2F performed the lowest efficiency of 0.97% as the donor and the highest efficiency of 2.65% as the acceptor. The electron-donating and electron-withdrawing property of M-1F are in-between that of M-0F and M-2F. Among the three molecules, the electron mobility is increased while the hole mobility is decreased with increasing fluorination. This work provides a typical example of tuning of the electron donating and withdrawing property without changes to the backbone of the conjugated molecules, which is important for further designing high performance solution processable small molecules.

Enhancing Performance of Large-Area Organic Solar Cells with Thick Film via Ternary Strategy.

Large-scale fabrication of organic solar cells requires an active layer with high thickness tolerability and the use of environment-friendly solvents. Thick films with high-performance can be achieved via a ternary strategy studied herein. The ternary system consists of one polymer donor, one small molecule donor, and one fullerene acceptor. The small molecule enhances the crystallinity and face-on orientation of the active layer, leading to improved thickness tolerability compared with that of a polymer-fullerene binary system. An active layer with 270 nm thickness exhibits an average power conversion efficiency (PCE) of 10.78%, while the PCE is less than 8% with such thick film for binary system. Furthermore, large-area devices are successfully fabricated using polyethylene terephthalate (PET)/Silver gride or indium tin oxide (ITO)-based transparent flexible substrates. The product shows a high PCE of 8.28% with an area of 1.25 cm2 for a single cell and 5.18% for a 20 cm2 module. This study demonstrates that ternary organic solar cells exhibit great potential for large-scale fabrication and future applications.

Fluorination-enabled optimal morphology leads to over 11% efficiency for inverted small-molecule organic solar cells.

Solution-processable small molecules for organic solar cells have attracted intense attention for their advantages of definite molecular structures compared with their polymer counterparts. However, the device efficiencies based on small molecules are still lower than those of polymers, especially for inverted devices, the highest efficiency of which is <9%. Here we report three novel solution-processable small molecules, which contain π-bridges with gradient-decreased electron density and end acceptors substituted with various fluorine atoms (0F, 1F and 2F, respectively). Fluorination leads to an optimal active layer morphology, including an enhanced domain purity, the formation of hierarchical domain size and a directional vertical phase gradation. The optimal morphology balances charge separation and transfer, and facilitates charge collection. As a consequence, fluorinated molecules exhibit excellent inverted device performance, and an average power conversion efficiency of 11.08% is achieved for a two-fluorine atom substituted molecule.

Acceptor End-Capped Oligomeric Conjugated Molecules with Broadened Absorption and Enhanced Extinction Coefficients for High-Efficiency Organic Solar Cells.

Acceptor end-capping of oligomeric conjugated molecules is found to be an effective strategy for simultaneous spectral broadening, extinction coefficient enhancement, and energy level optimization, resulting in profoundly enhanced power conversion efficiencies (of 9.25% and 8.91%) compared to the original oligomers. This strategy is effective in overcoming the absorption disadvantage of oligomers and small molecules due to conjugation limitation.

Synergistic effect of polymer and small molecules for high-performance ternary organic solar cells.

A ternary blend system with two donors and one acceptor provides an effective route to improve the performance of organic solar cells. A synergistic effect of polymer and small molecules is observed in ternary solar cells, and the power conversion efficiency (PCE) of the ternary system (8.40%) is higher than those of binary systems based on small molecules (7.48%) or polymers (6.85%).

Improving the Performances of Random Copolymer Based Organic Solar Cells by Adjusting the Film Features of Active Layers Using Mixed Solvents.

A novel random copolymer based on donor⁻acceptor type polymers containing benzodithiophene and dithienosilole as donors and benzothiazole and diketopyrrolopyrrole as acceptors was designed and synthesized by Stille copolymerization, and their optical, electrochemical, charge transport, and photovoltaic properties were investigated. This copolymer with high molecular weight exhibited broad and strong absorption covering the spectra range from 500 to 800 nm with absorption maxima at around 750 nm, which would be very conducive to obtaining large short-circuits current densities. Unlike the general approach using single solvent to prepare the active layer film, mixed solvents were introduced to change the film feature and improve the morphology of the active layer, which lead to a significant improvement of the power conversion efficiency. These results indicate that constructing random copolymer with multiple donor and acceptor monomers and choosing proper mixed solvents to change the characteristics of the film is a very promising way for manufacturing organic solar cells with large current density and high power conversion efficiency.

Linked-Acceptor Type Conjugated Polymer for High Performance Organic Photovoltaics with an Open-Circuit Voltage Exceeding 1 V.

A linked-acceptor type conjugated polymer is designed and sythesized based on 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (BDTT) and linked-thieno[3,4-c]pyrrole-4,6-dione (LTPD). This polymer uses alkyl-substituted thiophene as a bridge. The PBDTT-LTPD includes two TPD units in one repeating unit, which can enhance acceptor density in the polymer backbone and lower the highest occupied molecular orbital (HOMO) level. By contrast, variable alkyl substitutions in the thiophene-bridges ensure the subtle regulation of polymer properties. The solar cells based on PBDTT-LTPD display an open-circuit voltage (Voc) that exceeds 1 V, and a maximum power conversion efficiency (PCE) of 7.59% is obtained. This PCE value is the highest for conventional single-junction bulk heterojunction solar cells with Voc values of up to 1 V. Given that PBDTT-LTPD exhibits a low HOMO energy level and a band gap equivalent to that of poly(3-hexylthiophene), PBDTT-LTPD/phenyl-C61-butyric acid methyl ester may be a promising candidate for the front cell in tandem polymer solar cells.