Environmentally Friendly Solvent‐Processed Organic Solar Cells that are Highly Efficient and Adaptable for the Blade‐Coating Method

The power conversion efficiencies (PCEs) of state‐of‐the‐art organic solar cells (OSCs) have increased to over 13%. However, the most commonly used solvents for making the solutions of photoactive materials and the coating methods used in laboratories are not adaptable for future practical production. Therefore, taking a solution‐coating method with environmentally friendly processing solvents into consideration is critical for the practical utilization of OSC technology. In this study, a highly efficient PBTA‐TF:IT‐M‐based device processed with environmentally friendly solvents, tetrahydrofuran/isopropyl alcohol (THF/IPA) and o‐xylene/1‐phenylnaphthalene, is fabricated; a high PCE of 13.1% can be achieved by adopting the spin‐coating method, which is the top result for OSCs. More importantly, a blade‐coated non‐fullerene OSC processed with THF/IPA is demonstrated for the first time to obtain a promising PCE of 11.7%; even for the THF/IPA‐processed large‐area device (1.0 cm²) made by blade‐coating, a PCE of 10.6% can still be maintained. These results are critical for the large‐scale production of highly efficient OSCs in future studies.     

Large‐Area Organic Solar Cells: Material Requirements,Modular Designs,and Printing Methods

The printing of large‐area organic solar cells (OSCs) has become a frontier for organic electronics and is also regarded as a critical step in their industrial applications. With the rapid progress in the field of OSCs, the highest power conversion efficiency (PCE) for small‐area devices is approaching 15%, whereas the PCE for large‐area devices has also surpassed 10% in a single cell with an area of ≈1 cm². Here, the progress of this fast developing area is reviewed, mainly focusing on: 1) material requirements (materials that are able to form efficient thick active layer films for large‐area printing); 2) modular designs (effective designs that can suppress electrical, geometric, optical, and additional losses, leading to a reduction in the PCE of the devices, as a consequence of substrate area expansion); and 3) printing methods (various scalable fabrication techniques that are employed for large‐area fabrication, including knife coating, slot‐die coating, screen printing, inkjet printing, gravure printing, flexographic printing, pad printing, and brush coating). By combining thick‐film material systems with efficient modular designs exhibiting low‐efficiency losses and employing the right printing methods, the fabrication of large‐area OSCs will be successfully realized in the near future.     

高分子自组装掩膜的制备

利用高分子共混物的微相分离和自组装原理,采用溶液共混和旋转涂膜的方法制得聚苯乙烯/聚甲基丙烯酸甲酯(PS/PMMA)高分子共混物薄膜,对薄膜经过再加工得到具有纳米微孔的PMMA薄膜,研究了对溶液进行超声处理的时间、PS/PMMA共混物溶液浓度、旋涂转速和试片表面对掩膜形貌的影响。以此PMMA薄膜为掩膜对GaP表面进行湿法腐蚀,得到一种蜂窝状的表面微结构,它能使发光二极管(LED)的光功率平均提高18%。     

导电聚合物MEH-PPV表面光电特性的研究

用接触电位差(CPD)方法研究了导电聚合物MEH-PPV薄膜的光电特性，测得MEH-PPV的能隙为2．1eV，表面功函数为4．7-4．8eV，是p型导电材料，同时研究了不同铸膜溶剂对薄膜光电特性的影响，测得由不含芳环的四氢呋喃为溶剂制得的薄膜表面功函数比由含芳环的氯苯为溶剂制得的薄膜低0．15eV。     

Deposition and corrosion behavior of silicate conversion coatings on aluminum alloy 2024

Potassium silicate was deposited on AA2024 aluminum alloy as environmentally friendly conversion coatings and its corrosion behavior were examined by means of electrochemical impedance spectroscopy, potentiodynamic polarization and surfaces techniques. Potentiodynamic polarization curves show significant decrease in corrosion current density of silicate coated aluminum in NaCl solution. The corrosion resistance was increased with increasing silicate concentration of coating baths. The results indicated that the coating applied from 3 molar silicate baths is more uniform and continuous. The X‐ray diffraction (XRD) and energy discharge spectroscopy (EDS) spectra confirm the existence of silicate film on the AA2024 surface. The coating performance was evaluated in acidic and basic NaCl solution and the results show the stability of silicate conversion coating in these solutions.     

Graphdiyne Derivative as Multifunctional Solid Additive in Binary Organic Solar Cells with 17.3% Efficiency and High Reproductivity

Morphology tuning of the blend film in organic solar cells (OSCs) is a key approach to improve device efficiencies. Among various strategies, solid additive is proposed as a simple and new way to enable morphology tuning. However, there exist few solid additives reported to meet such expectations. Herein, chlorine-functionalized graphdiyne (GCl) is successfully applied as a multifunctional solid additive to fine-tune the morphology and improve device efficiency as well as reproductivity for the first time. Compared with 15.6% efficiency for control devices, a record high efficiency of 17.3% with the certified one of 17.1% is obtained along with the simultaneous increase of short-circuit current (J_sc) and fill factor (FF), displaying the state-of-the-art binary organic solar cells at present. The redshift of the film absorption, enhanced crystallinity, prominent phase separation, improved mobility, and decreased charge recombination synergistically account for the increase of J_sc and FF after introducing GCl into the blend film. Moreover, the addition of GCl dramatically reduces batch-to-batch variations benefiting mass production owing to the nonvolatile property of GCl. All these results confirm the efficacy of GCl to enhance device performance, demonstrating a promising application of GCl as a multifunctional solid additive in the field of OSCs.     

A 3‐Fluoro‐4‐hexylthiophene‐Based Wide Bandgap Donor Polymer for 10.9% Efficiency Eco‐Friendly Nonfullerene Organic Solar Cells

Nonfullerene organic solar cells (NFOSCs) are attracting increasing academic and industrial interest due to their potential uses for flexible and lightweight products using low‐cost roll‐to‐roll technology. In this work, two wide bandgap (WBG) polymers, namely P(fTh‐BDT)‐C6 and P(fTh‐2DBDT)‐C6, are designed and synthesized using benzodithiophene (BDT) derivatives. Good oxidation stability and high solubility are achieved by simultaneously introducing fluorine and alkyl chains to a single thiophene (Th) unit. Solid P(fTh‐2DBDT)‐C6 films present WBG optical absorption, suitable frontier orbital levels, and strong π–π stacking effects. In addition, P(fTh‐2DBDT)‐C6 exhibits good solubility in both halogenated and nonhalogenated solvents, suggesting its suitability as donor polymer for NFOSCs. The P(fTh‐2DBDT)‐C6:3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone))‐5,5,11,11‐tetrakis(5‐hexylthienyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene (ITIC‐Th) based device processed using chlorobenzene/1,8‐diiodooctane (CB/DIO) exhibits a remarkably high power conversion efficiency (PCE) of 11.1%. Moreover, P(fTh‐2DBDT)‐C6:ITIC‐Th reaches a high PCE of 10.9% when processed using eco‐friendly solvents, such as o‐xylene/diphenyl ether (DPE). The cell processed using CB/DIO maintains 100% efficiency after 1272 h, while that processed using o‐xylene/DPE presents a 101% increase in efficiency after 768 h and excellent long‐term stability. The results of this study demonstrate that simultaneous fluorination and alkylation are effective methods for designing donor polymers appropriate for high‐performance NFOSCs.     

High‐Efficiency All‐Small‐Molecule Organic Solar Cells Based on an Organic Molecule Donor with Alkylsilyl‐Thienyl Conjugated Side Chains

Two medium‐bandgap p‐type organic small molecules H21 and H22 with an alkylsily‐thienyl conjugated side chain on benzo[1,2‐b:4,5‐b′]dithiophene central units are synthesized and used as donors in all‐small‐molecule organic solar cells (SM‐OSCs) with a narrow‐bandgap n‐type small molecule 2,2′‐((2Z,2′Z)‐((4,4,9,9‐tetrahexyl‐4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐2,7‐diyl)bis(methanylylidene))bis(3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile (IDIC) as the acceptor. In comparison to H21 with 3‐ethyl rhodanine as the terminal group, H22 with cyanoacetic acid esters as the terminal group shows blueshifted absorption, higher charge‐carrier mobility and better 3D charge pathway in blend films. The power conversion efficiency (PCE) of the SM‐OSCs based on H22:IDIC reaches 10.29% with a higher open‐circuit voltage of 0.942 V and a higher fill factor of 71.15%. The PCE of 10.29% is among the top efficiencies of nonfullerene SM‐OSCs reported in the literature to date.     

一种新型的水性丙烯酸长余辉发光涂料

以Eu^2 和Dy^3 共掺杂的铝酸锶发光材料为发光体，以水性丙烯酸乳液为成膜介质制备了一种新型的发光涂料。该发光涂料环境友好，而且比相应的发光材料具有更长的余辉发光时间和更高的发光强度。     

Organic Photovoltaic Cells: From Performance Improvement to Manufacturing Processes

Organic photovoltaics (OPVs) have been pursued as a next generation power source due to their light weight, thin, flexible, and simple fabrication advantages. Improvements in OPV efficiency have attracted great attention in the past decade. Because the functional layers in OPVs can be dissolved in common solvents, they can be manufactured by eco‐friendly and scalable printing or coating technologies. In this review article, the focus is on recent efforts to control nanomorphologies of photoactive layer and discussion of various solution‐processed charge transport and extraction materials, to maximize the performance of OPV cells. Next, recent works on printing and coating technologies for OPVs to realize solution processing are reviewed. The review concludes with a discussion of recent advances in the development of non‐traditional lamination and transfer method towards highly efficient and fully solution‐processed OPV.     

Fabrication of a novel organic polymer thin film

Fabrication of organic polymer thin films and organic semiconductors are critical for the development of sophisticated organic thin film based devices. Radio Frequency plasma polymerisation is a well developed and widely used fabrication technique for polymer thin films. This paper describes the fabrication of an organic polymer thin film from a monomer based on Lavandula angustifolia. Several polymer thin films were manufactured with thicknesses ranging from 200 nm to 2400 nm. The energy gap of the polymer thin film was measured to be 2.93 eV. The refractive index and extinction coefficient was determined to be 1.565 (at 500 nm) and 0.01 (at 500 nm) respectively. The organic polymer thin film demonstrates the possibility of an environmentally friendly, cost effective organic semiconductor.     

Preparation and structure of fluorinated/non-fluorinated polyacrylate gradient emulsion blend film

The emulsion blend method, which is environmentally friendly and energy saving, was used to prepare a compositional gradient film of fluorinated/non-fluorinated polyacrylate in this paper. The size and glass-transition temperature (T_g) of the emulsion particles were designed to enhance the driving force of their selective congregation and promote the formation of gradient structure. The structures and surface properties of the obtained films were characterized. The results showed that when the fluorinated components have much smaller particle size and higher T_g than those of fluorine-free polyacrylate components, the gradient structures formed in the direction across the film thickness of the films. The concentration of the fluorinated component increased gradually from film-glass interface to film-air interface in the blend film, making the surface free energies of the two sides of the gradient film distinctively different.     

Halogen-Free Donor Polymers Based on Dicyanobenzotriazole with Low Energy Loss and High Efficiency in Organic Solar Cells

Halogenation of organic semiconductors is an efficient strategy for improving the performance of organic solar cells (OSCs), while the introduction of halogens usually involves complex synthetic process and serious environment pollution problems. Herein, three halogen-free ternary copolymer donors (PCNx, x = 3, 4, 5) based on electron-withdrawing dicyanobenzotriazole are reported. When blended with the Y6, PCN3 with strong interchain interactions results in appropriate crystallinity and thermodynamic miscibility of the blend film. Grazing-incidence wide-angle X-ray scattering measurements indicate that PCN3 has more ordered arrangement and stronger π–π stacking than previous PCN2. Fourier-transform photocurrent spectroscopy and external quantum efficiency of electroluminescence measurements show that PCN3-based OSCs have lower energy loss than PCN2, which leads to their higher open-circuit voltage (0.873 V). The device based on PCN3 reaches power conversion efficiency (PCE) of 15.33% in binary OSCs, one of the highest values for OSCs with halogen-free donor polymers. The PCE of 17.80% and 18.10% are obtained in PM6:PCN3:Y6 and PM6:PCN3:BTP-eC9 ternary devices, much higher than those of PM6:Y6 (16.31%) and PM6:BTP-eC9 (17.33%) devices. Additionally, this ternary OSCs exhibit superior stability compared to binary host system. This work gives a promising path for halogen-free donor polymers to achieve low energy loss and high PCE.     

Sustainable betalain pigments as eco-friendly film coating over aluminium surface

Sustainable betalain pigments extracted from beetroots were used as eco-friendly film coating over aluminium surface. The film coating was examined and verified by corrosive 1.0 M HCl solution. Characterization of chemical structure of the betalain pigments was done using spectroscopic attenuated total reflectance Fourier transform infrared (ATR-FTIR) and UV–Vis technique. Scanning electron microscope technique was used to demonstrate the eco-friendly film coating before and after been examined via corrosive 1.0 M HCl solution. Various operating conditions were studied to meet highest inhibition efficiency values such as betalain concentration, operating temperature and turbulent flow, and maximum inhibition efficiency?=?98.4% was displayed. Multiple adsorption isotherms like Langmuir, Temkin, and Freundlich were used effectively to determine equilibrium constants and adsorption parameters. Dynamic investigations revealed a decline of rate of corrosion (R_C) and rise of activation energy values (E_a) at higher betalain concentrations. Thermodynamic investigations revealed physisorption process, exothermic enthalpy, and low entropic values of betalain on aluminium surface. The noticeable specifications of low cost, abundance and sustainability, environmentally friendly, and high technical feasibility of betalain pigments adapt them to be the futuristic outstanding sustainable film coating for metal surfaces.

Graphical abstract

     

Two Well‐Miscible Acceptors Work as One for Efficient Fullerene‐Free Organic Solar Cells

High‐performance ternary organic solar cells are fabricated by using a wide‐bandgap polymer donor (bithienyl‐benzodithiophene‐alt‐fluorobenzotriazole copolymer, J52) and two well‐miscible nonfullerene acceptors, methyl‐modified nonfullerene acceptor (IT‐M) and 2,2′‐((2Z ,2′Z )‐((5,5′‐(4,4,9,9‐tetrakis(4‐hexylphenyl)‐4,9‐dihydros‐indaceno[1,2‐b :5,6‐b ′]dithiophene‐2,7‐diyl)bis(4‐((2‐ethylhexyl)oxy)thiophene‐5,2‐diyl))bis(methanylylidene))bis(3‐oxo‐2,3‐dihydro‐1H ‐indene‐2,1‐diylidene))dimalononitrile (IEICO). The two acceptors with complementary absorption spectra and similar lowest unoccupied molecular orbital levels show excellent compatibility in the blend due to their very similar chemical structures. Consequently, the obtained ternary organic solar cells (OSC) exhibits a high efficiency of 11.1%, with an enhanced short‐circuit current density of 19.7 mA cm^?2 and a fill factor of 0.668. In this ternary system, broadened absorption, similar output voltages, and compatible morphology are achieved simultaneously, demonstrating a promising strategy to further improve the performance of ternary OSCs.     

铝合金表面化学转化技术的研究进展

随着环保要求的不断提高,传统的含铬化学转化膜已不能满足工业生产的要求,开发新型无铬环保的铝合金转化处理技术,已成为研究热点。研究表明,以新型无机盐和稀土为成膜物质的化学转化膜具有优良的表面防护能力。综述了当前新型化学转化技术的研究现状,介绍了无机和稀土转化膜的研究进展,分析了转化膜的性能特点,指出了当前化学转化处理技术存在的问题,展望了化学转化技术的发展趋势,明确了无机盐及稀土的用量对转化膜性能的影响、转化液中辅助物质对转化膜的影响是今后研究的方向。     

Green fabrication of agar-conjugated Fe3O4 magnetic nanoparticles

Magnetic nanoparticles are of great interest both for fundamental research and emerging applications. In the biomedical field, magnetite (Fe(3)O(4)) has shown promise as a hyperthermia-based tumor therapeutic. However, preparing suitable solubilized magnetite nanoparticles is challenging, primarily due to aggregation and poor biocompatibility. Thus methods for coating Fe(3)O(4) NPs with biocompatible stabilizers are required. We report a new method for preparing Fe(3)O(4) nanoparticles by co-precipitation within the pores of agar gel samples. Permeated agar gels were then dried and ground into a powder, yielding agar-conjugated Fe(3)O(4) nanoparticles. Samples were characterized using XRD, FTIR, TGA, TEM and SQUID. This method for preparing agar-coated Fe(3)O(4) nanoparticles is environmentally friendly, inexpensive and scalable.     

Effectiveness of barrier film with a cellulose coating that carries nisin blends for the inhibition of listeria monocytogenes

The objective of this study was to determine the effectiveness of two nisin blend antimicrobial agents (Guardian NR 250, Novagard CBI) incorporated into a cellulose coating that was applied onto a barrier film against Listeria monocytogenes. The minimum inhibitory concentration (MIC) of the agents in solution against L. monocytogenes was found to be 2.74 mg/ml for the two nisin blends. The concentrations tested for both nisin blend treatments were 5.49, 10.9, 16.4 and 21.9 mg/ml. Guardian NR 250 resulted in wider zones of inhibition compared to the Novagard CBI at all levels tested. The MIC for Guardian NR 250 in the film was 5.49 mg/ml. Films containing Novagard CBI did not show any antimicrobial activity. A food challenge study was conducted using the film containing Guardian NR 250 at levels of 5.49 and 21.9 mg/ml. Inoculated fresh beef cubes were individually packaged with pre‐made barrier film pouches that had an interior cellulose coating containing the antimicrobial agent and stored at 4°C for 36 days. Bacterial colonies were enumerated every 6 days on modified Oxford agar. There was no significant difference in the L. monocytogenes population between two levels of Guardian NR 250 throughout the study. There was statistically significant inhibition of L. monocytogenes for both levels of Guardian NR 250 during 18–30 days of storage compared to a control film without the antimicrobial agent. Copyright © 2010 John Wiley & Sons, Ltd.     

Study of the microstructure of inkjet-printed P3HT:PCBM blend for photovoltaic applications

Recently, great interest has been devoted to cost-effective alternative energy sources such as organic solar cells because of the mechanical flexibility and the versatility of chemical structure, the low cost of fabrication, and ease of processing. As regards this last point, the possibility to deposit organic materials from solutions at low temperatures makes them employable for fabricating printed solar cells by direct printing methods. In this study, we used the inkjet-printing technology to deposit P3HT blends with various fullerene acceptors ([60]PCBM, [70]PCBM and bis[60]PCBM) dissolved in single solvents, 1,2-dichlorobenzene (DCB) and chlorobenzene (CB), and their mixtures. After optimizing the printing parameters (printhead speed, drop emission frequency, and substrate temperature), the effect of the solvents on the morphology of the photoactive layers was analyzed through Raman spectroscopy and atomic force microscopy. Polymer solar cells with the structure glass/ITO/PEDOT:PSS/blend/Ca/Al were fabricated and characterized by current–voltage (I–V) measurements under 100 mW/cm² AM 1.5G illumination. A comparative study of the performances of the devices was performed based on three different fullerene derivatives, correlating them to the microstructure of the printed blend films. The optimal devices were obtained when the blend films were deposited from a mixture of DCB:CB 4:1 by volume: this was in agreement with the most favorable morphology of these films.     

Aggregation‐Induced Multilength Scaled Morphology Enabling 11.76% Efficiency in All‐Polymer Solar Cells Using Printing Fabrication

All‐polymer solar cells (all‐PSCs) exhibit excellent stability and readily tunable ink viscosity, and are therefore especially suitable for printing preparation of large‐scale devices. At present, the efficiency of state‐of‐the‐art all‐PSCs fabricated by the spin‐coating method has exceeded 11%, laying the foundation for the preparation and practical utilization of printed devices. A high power conversion efficiency (PCE) of 11.76% is achieved based on PTzBI‐Si:N2200 all‐PSCs processing with 2‐methyltetrahydrofuran (MTHF, an environmentally friendly solvent) and preparation of active layers by slot die printing, which is the top efficient for all‐PSCs. Conversely, the PCE of devices processed by high‐boiling point chlorobenzene is less than 2%. Through the study of film formation kinetics, volatile solvents can freeze the morphology in a short time, and a more rigid conformation with strong intermolecular interaction combined with the solubility limit of PTzBI‐Si and N2200 in MTHF results in the formation of a fibril network in the bulk heterojunction. The multilength scaled morphology ensures fast transfer of carriers and facilitates exciton separation, which boosts carrier mobility and current density, thus improving the device performance. These results are of great significance for large‐scale printing fabrication of high‐efficiency all‐PSCs in the future.