Theoretical characterization and design of small molecule donor material containing naphthodithiophene central unit for efficient organic solar cells

To seek for high‐performance small molecule donor materials used in heterojunction solar cell, six acceptor–donor–acceptor small molecules based on naphtho[2,3‐b:6,7‐b′]dithiophene ( NDT ) units with different acceptor units were designed and characterized using density functional theory and time‐dependent density functional theory. Their geometries, electronic structures, photophysical, and charge transport properties have been scrutinized comparing with the reported donor material NDT(TDPP)₂ ( TDPP = thiophene‐capped diketopyrrolopyrrole). The open circuit voltage (V_oc), energetic driving force(ΔE_L‐L), and exciton binding energy (E_b) were also provided to give an elementary understanding on their cell performance. The results reveal that the frontier molecular orbitals of 3–7 match well with the acceptor material PC₆₁BM , and compounds 3–5 were found to exhibit the comparable performances to 1 and show promising potential in organic solar cells. In particular, comparing with 1 , system 7 with naphthobisthiadiazole acceptor unit displays broader absorption spectrum, higher V_oc, lower E_b, and similar carrier mobility. An in‐depth insight into the nature of the involved excited states based on transition density matrix and charge density difference indicates that all S₁ states are mainly intramolecular charge transfer states with the charge transfer from central NDT unit to bilateral acceptor units, and also imply that the exciton of 7 can be dissociated easily due to its large extent of the charge transfer. In a word, 7 maybe superior to 1 and may act as a promising donor candidate for organic solar cell. © 2013 Wiley Periodicals, Inc.     

A naphthodithiophene-diketopyrrolopyrrole donor molecule for efficient solution-processed solar cells

We report the synthesis, characterization, and first implementation of a naphtho[2,3-b:6,7-b']dithiophene (NDT)-based donor molecule in highly efficient organic photovoltaics (OPVs). When NDT(TDPP)(2) (TDPP = thiophene-capped diketopyrrolopyrrole) is combined with the electron acceptor PC(61)BM, a power conversion efficiency (PCE) of 4.06 ± 0.06% is achieved-a record for a PC(61)BM-based small-molecule OPV. The substantial PCE is attributed to the broad, high oscillator strength visible absorption, the ordered molecular packing, and an exceptional hole mobility of NDT(TDPP)(2).     

Synthesis,characterization, and organic field‐effect transistors study of conjugated D–A copolymers based on dialkylated naphtho[1,2‐b:5,6‐b′]dithiophene/naphtho[1,2‐b:5,6‐b′]difuran and benzodiathiazole/benzoxadiazole

In this report, four donor–acceptor copolymers, P(NDT3‐BT), P(NDT3‐BO), P(NDF3‐BT), and P(NDF3‐BO), using 5,10‐didodecyl‐naphtho[1,2‐b:5,6‐b′]dithiophene (NDT3) or 5,10‐didodecyl‐naphtho[1,2‐b:5,6‐b′]difuran (NDF3) as an electron‐rich unit and benzodiathiazole (BT) or benzoxadiazole (BO) as an electron‐deficient one, were designed, synthesized, and characterized. Detailed systematical investigation was developed for studying the effect of the S/O atoms on the optical, electrochemical, and morphological properties of the polymers, as well as the subsequent performance of the organic field‐effect transistors (OFETs) fabricated from these copolymers. It was found that, compared with NDF3‐based P(NDF3‐BT)/P(NDF3‐BO), by replacing NDF3 with stronger aromatic NDT3, the resultant P(NDT3‐BT)/P(NDT3‐BO) show smaller lamellar distance with an increased surface roughness in solid state, and relatively higher hole mobilities are obtained. The hole mobilities of the four polymers based on OFETs varied from 0.20 to 0.32 cm² V^?1 s^?1 depending on their molecular structures, giving some valuable insights for the further design and development of a new generation of semiconducting materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2465–2476     

Contrôle non destructif de matériaux composites par la technique des courants de foucault : une nouvelle approche

Quality testing of composite materials is regularly carried out using non-destructive testing (NDT) techniques such as ultrasound, radiography or infrared thermography. However, these techniques present some limitations for the NDT of composites in terms of accuracy, sensitivity, repeatability of the signal and sometimes difficulty of calibration. In this article, it is demonstrated that eddy current testing, once solely dedicated for NDT of metallic materials, can also be adapted for the examination of composite materials. Indeed, this technique appears to be adequate for the detection and the characterisation of major flaws such as delamination and impact. A good reproducibility of the signals has been observed and this technique may become an efficient and low cost alternative compared to more complex and expensive techniques. Experimental results are shown and analysed and the advantages and limitations of eddy current testing of composite materials are discussed.     

Molecular Stacking and Aggregation Optimization of Photoactive Layer through Solid Additive Enables High-Performance Organic Solar Cells

Regulating molecular packing and aggregation of photoactive layer is a critical but challenging issue in developing high-performance organic solar cells. Herein, two structurally similar analogues of anthra[2,3-b : 6,7-b′]dithiophene (ADT) and naphtho[1,2-b : 5,6-b′]dithiophene (NDT) are developed as solid additive to exploit their effect in regulating the molecular aggregation and π-stacking of photoactive layer. We clarify that the perpendicular arrangements of NDT can enlarge the molecular packing space and improve the face-on stacking of Y6 during the film formation, favoring a more compact and ordered long-range π-π stacking in the out-of-plane direction after the removal of NDT under thermal annealing. The edge-to-face stacked herringbone-arrangement of ADT along with its non-volatilization under thermal annealing can induce the coexistence of face-on and edge-on stacking of blend film. As a result, the NDT treatment shows encouraging effect in improving the photovoltaic performance of devices based on various systems. Particularly, a remarkable PCE of 18.85 % is achieved in the PM6 : L8-BO-based device treated by NDT additive, which is a significant improvement with regard to the PCE of 16.41 % for the control device. This work offers a promising strategy to regulate the molecular packing and aggregation of photoactive layer towards significantly improved performance and stability of organic solar cells.     

Advances in Organic Near‐Infrared Materials and Emerging Applications

Much progress has been made in the field of research on organic near‐infrared materials for potential applications in photonics, communications, energy, and biophotonics. This account mainly describes our research work on organic near‐infrared materials; in particular, donor‐acceptor small molecules, organometallics, and donor‐acceptor polymers with the bandgaps less than 1.2 eV. The molecular designs, structure‐property relationships, unique near‐infrared absorption, emission and color/wavelength‐changing properties, and some emerging applications are discussed.     

Conjugation expansion strategy enables highly stable all-polymer solar cells

The stability issue is one of the key factors hindering the commercial application of organic solar cells. All-polymer organic solar cell is one of the effective ways to solve the stability problem. In this work, we designed and synthesized two polymer donor materials PBDT and PDTBDT with different conjugation ranges, and demonstrated for the first time that extending the conjugation range of donor materials in all polymer solar cells can significantly improve device efficiency and stability. The experimental results of materials and devices show that PDTBDT with a larger conjugation range has stronger crystallinity and a more planar structure, which endows the active layer in its corresponding device with higher exciton dissociation probability, lower carrier recombination probability, more balanced charge transport properties and more favorable film morphology. As a result, the PDTBDT:PYF-T-o devices display an outstanding PCE of 13.38%, which is much higher than PBDT with smaller conjugation range based devices. Moreover, the PDTBDT:PYF-T-o device retains 0.86 of the initial PCE after over 500 h in the air atmosphere, exhibiting significantly improved stability. The improved stability is attributed to the enhanced moisture and air tolerance of active layer film thanks to the strong crystallinity of the donor material. These results demonstrate that the conjugation expansion strategy is one of the effective ways to obtain efficient and stable all-polymer organic solar cells.     

可溶液加工给体-受体有机小分子太阳能电池材料研究进展

近年来,有机小分子体异质结太阳能电池因其制备工艺简单、廉价、轻便及柔性等优点而备受关注.理想的有机小分子给体材料是提高有机太阳能电池光电转换效率的基础.系统地综述了可溶液加工有机小分子太阳能电池给体材料的研究进展,并对其发展趋势和应用前景做了展望.     

Crystal Engineering of Dual Channel p/n Organic Semiconductors by Complementary Hydrogen Bonding

The supramolecular arrangement of organic semiconductors in the solid state is as critical for their device properties as the molecular structure, but is much more difficult to control. To enable supramolecular design of semiconducting materials, we introduced dipyrrolopyridine as a new donor semiconductor capable of complementary hydogen bonding with naphthalenediimide acceptors. Through a combination of solution, crystallographic, and device studies, we show that the self‐assembly driven by H bonding a) modulates the charge‐transfer interactions between the donor and acceptor, b) allows for precise control over the solid‐state packing, and c) leads to a combination of the charge‐transport properties of the individual components. The predictive power of this approach was demonstrated in the synthesis of three new coassembled materials which show both hole and electron transport in single‐crystal field‐effect transistors. These studies provide a foundation for advanced solid‐state engineering in organic electronics, capitalizing on the complementary H bonding.     

Manipulation of Triplet Excited States in Two-Component Systems for High-Performance Organic Afterglow Materials

The past several years have witnessed the tremendous development of novel chemical structures, new design strategies and intriguing applications in the field of room-temperature phosphorescence (RTP) and organic afterglow materials. This Review article focuses on recent advancements of high-performance organic afterglow materials obtained by two-component design strategies such as a dopant-matrix, donor–acceptor, sensitization, and energy-transfer strategies. Based on some cutting-edge studies, organic afterglow efficiency has been largely improved, exceeding 90 % in several cases. Organic afterglow durations reach tens of seconds in phosphorescence systems and hours in donor–acceptor systems. Organic afterglow brightness outcompetes some inorganic afterglow materials in the first several seconds after ceasing excitation source. Organic afterglow colors cover the whole visible regions and extend to near-infrared regions with respectful afterglow efficiency. On the basis of these achievements, researchers demonstrate promising applications of organic afterglow materials in diverse fields, which has also been reviewed.     

A-π-D-π-A small-molecule donors with different end alkyl chains obtain different morphologies in organic solar cells

The small molecular donors with different end alkyl chains provide appropriate phase separation and molecular stacking orientation for all-small-molecule solar cells. The power conversion efficiency (PCE) have been improved obviously, and the highest PCE reaches 7.06%. The results demonstrate that the optimized end alkyl chains can be used to design A-π-D-π-A backbone structure small molecular electron donors for small-molecule organic solar cells.     

Recent Advances in Isoindigo‐Inspired Organic Semiconductors

Over the past decade, isoindigo has become a widely used electron‐deficient subunit in donor‐acceptor organic semiconductors, and these isoindigo‐based materials have been widely used in both organic photovoltaic (OPV) devices and organic field effect transistors (OFETs). Shortly after the development of isoindigo‐based semiconductors, researchers began to modify the isoindigo structure in order to change the optoelectronic properties of the resulting materials. This led to the development of many new isoindigo‐inspired compounds; since 2012, the Kelly Research Group has synthesized a number of these isoindigo analogues and produced a variety of new donor‐acceptor semiconductors. In this Personal Account, recent progress in the field is reviewed. We describe how the field has evolved from relatively simple donor‐acceptor small molecules to structurally complex, highly planarized polymer systems. The relevance of these materials in OPV and OFET applications is highlighted, with particular emphasis on structure‐property relationships.     

Design of bicontinuous donor/acceptor morphologies for use as organic solar cell active layers

In recent works, we demonstrated the achievement of bicontinuous donor/acceptor morphologies by the addition of conjugated block copolymers to a blend of conjugated homopolymer donors and fullerene acceptors. However, the domain sizes resulting in experiments were much larger than those of interest for high‐performance organic solar cells. Moreover, a significant concentration of fullerene acceptors was present in the donor domains. Here, we utilize simulations to study the bicontinuous donor/acceptor morphologies that result for different parametric conditions. Using such results, we provide guidelines for how to blend polymer materials to give rise to bicontinuous phases with the smaller and more compositionally pure domains that are desirable for organic photovoltaic applications. Our results can be generalized to treat a large range of donor and acceptor monomers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 884–895     

Naphtho[2,1‐b:3,4‐b′]dithiophene‐based Bulk Heterojunction Solar Cells: How Molecular Structure Influences Nanoscale Morphology and Photovoltaic Properties

Organic bulk heterojunction photovoltaic devices based on a series of three naphtho[2,1‐b:3,4‐b′]dithiophene (NDT) derivatives blended with phenyl‐C₇₁‐butyric acid methyl ester were studied. These three derivatives, which have NDT units with various thiophene‐chain lengths, were employed as the donor polymers. The influence of their molecular structures on the correlation between their solar‐cell performances and their degree of crystallization was assessed. The grazing‐incidence angle X‐ray diffraction and atomic force microscopy results showed that the three derivatives exhibit three distinct nanoscale morphologies. We correlated these morphologies with the device physics by determining the J–V characteristics and the hole and electron mobilities of the devices. On the basis of our results, we propose new rules for the design of future generations of NDT‐based polymers for use in bulk heterojunction solar cells.     

Emerging Light-Harvesting Materials Based on Organic Photovoltaic D/A Heterojunctions for Efficient Photocatalytic Water Splitting

Photocatalytic water splitting to hydrogen is a highly promising method to meet the surging energy consumption globally through the environmentally friendly means. As the initial step before photocatalysis, harvesting photons from sunlight is crucially important, thus making the design of photosensitizers with visible even near-infrared (NIR) absorptions get more and more attentions. In the past three years, organic donor/acceptor (D/A) heterojunctions with absorptions extending to 950 nm, have emerged as the new star light-harvesting materials for photocatalytic water splitting, demonstrating exciting advantages over inorganic materials in solar light utilization, hydrogen yielding rate, etc. This Minireview firstly gives a brief discussion about the principle processes and determining factors for photocatalytic water splitting with organic photovoltaic D/A heterojunction as photosensitizers. Thereafter, the current progress is summarized in details by introducing typical and excellent D/A heterojunction-based photocatalytic systems. Finally, not only the great prospects but also the most challenging issues confronted by organic D/A heterojunctions are indicated along with a perspective on the opportunities and new directions for future material explorations.     

Critical Role of Molecular Electrostatic Potential on Charge Generation in Organic Solar Cells

Revealing the charge generation is a crucial step to understand the organic photovoltaics. Recent development in non‐fullerene organic solar cells (OSCs) indicates efficient charge separation even with negligible energetic offset between the donor and acceptor materials. These new findings trigger a critical question concerning the charge separation mechanism in OSCs, traditionally believed to result from sufficient energetic offset between the polymer donor and fullerene acceptor. We propose a new mechanism, which involves the molecular electrostatic potential, to explain efficient charge separation in non‐fullerene OSCs. Together with the new mechanism, we demonstrate a record efficiency of ~12% for systems with negligible energetic offset between donor and acceptor materials. Our analysis also rationalizes different requirement of the energetic offset between fullerene‐based and non‐fullerene OSCs, and paves the way for further design of OSC materials with both high photocurrent and high photovoltage at the same time.     

非富勒烯聚合物太阳电池研究进展

综述了以p-型共轭聚合物为给体、n-型有机半导体为受体的非富勒烯聚合物太阳电池光伏材料最新研究进展,包括n-型共轭聚合物和可溶液加工小分子n-型有机半导体(n-OS)受体光伏材料,以及与之匹配的p-型共轭聚合物给体光伏材料.介绍的n-型共轭聚合物受体光伏材料包括基于苝酰亚胺(BDI)、萘酰亚胺(NDI)以及新型硼氮键连受体单元的D-A共聚物受体光伏材料,目前基于聚合物给体(J51)和聚合物受体(N2200)的全聚合物太阳电池的能量转换效率最高达到8.26%.n-OS小分子受体光伏材料包括基于BDI和NDI单元的有机分子、基于稠环中心给体单元的A-D-A型窄带隙有机小分子受体材料等.给体光伏材料包括基于齐聚噻吩和苯并二噻吩(BDT)给体单元的D-A共聚物,重点介绍与窄带隙A-D-A结构小分子受体吸收互补的、基于噻吩取代BDT单元的中间带隙二维共轭聚合物给体光伏材料.使用中间带隙的p-型共轭聚合物为给体、窄带隙A-D-A结构有机小分子为受体的非富勒烯聚合物太阳电池能量转换效率已经突破12%,展示了光明的前景.最后对非富勒烯聚合物太阳电池将来的发展进行了展望.     

Efficient light harvesting and energy transfer in organic-inorganic hybrid multichromophoric materials

Thin films of silica hybrid materials consisting of two to three covalently bound organic chromophores at different ratios were conveniently synthesized and fabricated. The photophysical properties of these materials have been studied. The fluorescence spectra reveal complete fluorescence resonance energy transfer (FRET) from donor to acceptor, and the light-harvesting ability of these hybrid materials increases with increasing the molar fraction of donor chromophore. In a three-chromophore system, the energy is transferred from 300 to 530 nm successfully. Time-resolved fluorescence experiments are employed to elucidate the average rates and efficiencies (84-97%) of energy transfer in these organic/inorganic hybrid systems. The hybrid materials have been shown to provide antenna effect to facilitate energy transfer and light harvesting.     

Molecular solubility and hansen solubility parameters for the analysis of phase separation in bulk heterojunctions

Although the fabrication procedures for bulk heterojunction (BHJ) solar cells are routinely optimized to accommodate new organic materials, the influence of solvent properties and cohesive forces on the film‐forming process and the self‐assembly of donor and acceptor molecules on the nanoscale are poorly understood. In this study, we measure the solubility of a variety of organic semiconductors in a range of solvents and calculate cohesive forces including dispersion forces, dipole interactions, and hydrogen bonding via Hansen Solubility Parameters (HSPs). HSPs were calculated by measuring the solubilities of various organic semiconductors in 27 solvents and the influence of solvent identity on film morphology of different BHJ mixtures was explored via atomic force microscopy (AFM). The possibility of correlations between HSPs and film morphology was considered; however, it is apparent that the HSP values alone do not play a critical role in determining the morphology of the films of conjugated polymers and molecules. This collection of solubility data constitutes the first of its type for organic semiconducting materials, and may act as a useful reference for the organic semiconductor community to aid in the understanding and selection of solvents for donor–acceptor BHJ mixtures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Fluorination vs. chlorination: a case study on high performance organic photovoltaic materials

Halogenation is a very efficient chemical modification method to tune the molecular energy levels, absorption spectra and molecular packing of organic semiconductors. Recently, in the field of organic solar cells(OSCs), both fluorine-and chlorinesubstituted photovoltaic materials, including donors and acceptors, demonstrated their great potentials in achieving high power conversion efficiencies(PCEs), raising a question that how to make a decision between fluorination and chlorination when designing materials. Herein, we systemically studied the impact of fluorination and chlorination on the properties of resulting donors(PBDB-T-2 F and PBDB-T-2 Cl) and acceptors(IT-4 F and IT-4 Cl). The results suggest that all the OSCs based on different donor and acceptor combinations can deliver good PCEs around 13%–14%. Chlorination is more effective than fluorination in downshifting the molecular energy levels and broadening the absorption spectra. The influence of chlorination and fluorination on the crystallinity of the resulting materials is dependent on their introduction positions. As chlorination has the advantage of easy synthesis, it is more attractive in designing low-cost photovoltaic materials and therefore may have more potential in largescale applications.