Effect of Arylmethylene Substitutions on Molecular Structure,Optoelectronic Properties and Photovoltaic Performance of Dithienocyclopentafluorene-Based Small-Molecule Acceptors

Two dithienocyclopentafluorene-based small-molecule acceptors (SMAs) were developed that feature methylene-functionalized conjugated side chains, to study the effect of arylmethylene substitution and its number on structure, optoelectronic properties and device performance. Results showed that two SMAs have better absorption properties and planarity, lower bandgaps and higher LUMOs compared with the control SMA without conjugated side chains. The synthesized SMAs were tested in polymer solar cells for examples of their applicability. This work argues that the introduction of methylene-functionalized conjugated side chains has great potential in tuning molecular structure, optoelectronic properties, device physics and photovoltaic performance of SMAs.     

Effect of substitution positions of alkyl side chains in phenanthrodithiophene–isoindigo copolymers: The enhancement of crystallinity and control of molecular orders

The synthesis, characterization, and solar cell application of newly developed two semiconducting polymers containing phenanthro[1,2‐b:8,7‐b′]dithiophene (PDT) and an isoindigo (IID) unit are described. In addition, a relationship between substitution position of side chains and molecular weights of the polymers and their solar cell performance are also discussed. Because of the installation of alkyl side chains onto sterically less hindered positions, PDT‐IID copolymers 12OD‐2 and 8OD‐2 have stronger intermolecular interaction than that of the previously reported copolymer 12OD . In low‐M_n polymers 12OD‐2 and 8OD‐2 formed high‐crystalline thin film with higher face‐on ratio than that of 12OD , but their unsuitable large‐scale phase separation suppressed their efficient photocurrent generation, leading to poor PCE of 2–3%. However, the surface morphology of 12OD‐2 and 8OD‐2 blended films are drastically improved by increasing M_n, which leads to the enhancement of J_sc and higher PCE of up to 4.3%. However, high‐M_n polymers 12OD‐2 and 8OD‐2 formed high‐crystalline film with about 10–15% lower face‐on ratio than that of high‐M_n polymer 12OD , leading to poor hole transporting ability, and thus lower J_sc and PCE. From this result, too much strong intermolecular interaction promotes the formation of unsuitable edge‐on orientation in blended films. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1757–1767     

Electrolytes for quasi solid‐state dye‐sensitized solar cells based on block copolymers

The first use of PS_n‐b‐PEO_m‐b‐PS_n block copolymers (PS = polystyrene, PEO = poly(ethylene oxide)) as solid hosts for iodine/iodide electrolytes in dye‐sensitized solar cells (DSSCs) is described. Using the benchmark photosensitizer N719, DSSC based on the quasi solid‐state electrolytes afforded efficiencies up to 6.7%, to be compared with an efficiency of 7.3% obtained in similar conditions with a conventional iodine/iodide liquid electrolyte. By varying the PS:PEO relative volume ratio in the block copolymers different properties and morphologies were obtained. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 719–727     

Recent advances of organometallic complexes in emerging photovoltaics

Organometallic complexes (OMCs) consisting of organic and metal active moieties have shown immense potential for application in solar cells. The diverse structure, rich porosity, and unique charge centers of OMCs enable them to be functional in solar cells. In this review, we introduced four types of OMCs, such as crown organometallic complexes, β-diketone metal complexes, cyclometallic complexes, and main chain metal-containing polymers, providing an in-depth analysis of the structure-performance relationship. OMCs could serve as active or interlayer materials in a variety of solar cell systems such as organic solar cells, perovskite solar cells, and dye-sensitized solar cells, especially some metals to improve the photoelectric performance of the device as dopants. In the end, perspectives on the opportunities and challenges of OMCs are given.     

Peculiar Photoinduced Electron Transfer in Porphyrin–Fullerene Akamptisomers

Porphyrin–fullerene dyads are promising candidates for organic photovoltaic devices. The electron-transfer (ET) properties of the molecular devices depend significantly on the mutual position of the donor and acceptor. Recently, a new type of molecular isomerism (akamptisomerism) has been discovered. In the present study, we explore how photoinduced ET can be modulated by passing from one akamptisomer to another. To this aim, four akamptisomers of the quinoxalinoporphyrin–[60]fullerene complex are selected for computational study. The most striking finding is that, depending on the isomer, the porphyrin unit in the dyad can act as either electron donor or electron acceptor. Thus, the stereoisomeric diversity allows one to change the direction of ET between the porphyrin and fullerene moieties. To understand the effect of akamptisomerism on the photoinduced ET processes, a detailed analysis of initial and final states involved in the ET is performed. The computed rate for charge separation is estimated to be in the region of 1–10 ns⁻¹. The formation of a long-living quinoxalinoporphyrin anion radical species is predicted.     

Dialkoxymethano[60]fullerenes as electron acceptors in thin-film organic solar cells

This study presents the synthesis, characterization, and electrochemical properties of four new dialkoxymethanofullerenes, as well as their performance in organic solar cells (OSCs) devices. Dialkoxymethanofullerenes were synthesized in 27%–32% yield by thermolysis of dialkoxyoxadiazolines and reaction with C₆₀ under reflux in toluene. The prepared compounds were then characterized and used for the first time as electron-acceptor materials in thin-film bulk heterojunction OSCs with PBTZT-stat-BDTT-8 as the electron donor material. The devices made with ethoxy-hexyloxymethanofullerene and methoxy-hexyloxymethanofullerene exhibited optimal power conversion efficiencies (PCEs) of 3.79% and 4.65%, with open-circuit voltage of 0.832 and 0.831 V, respectively. In contrast, the devices made with ethoxy-ethoxymethanofullerene and methoxy-ethoxymethanofullerene exhibited very low PCEs of <0.01% for both, indicating a large impact of the substituents on device performance.     

Molecular dynamics simulation of poly(3‐hexylthiophene) helical structure In Vacuo and in amorphous polymer surrounding

The stability of poly(3‐hexylthiophene) (P3HT) helical structure has been investigated in vacuo and in amorphous polymer surrounding via molecular dynamics‐based simulations at temperatures below and above the P3HT melting point. The results show that the helical chain remains stable at room temperature both in vacuo and in amorphous surrounding, and promptly loses its structure at elevated temperatures. However, the amorphous surrounding inhibits the destruction of the helix at higher temperatures. In addition, it is shown that the electrostatic interactions do not significantly affect the stability of the helical structure. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2448–2456     

实现均匀照度光伏聚光镜设计

为满足聚光光伏系统的聚光需求,解决传统点聚焦式聚光光伏系统中聚焦光斑不均匀、径长比过大和聚光比较小的缺点,在不增加二次匀光器件的前提下,设计了径长比小、聚焦光斑相对均匀、聚光比高的聚光光伏系统。根据几何光学柯勒照明原理、等光程原理和反射定律,通过数值求解等光程方程组获得聚光镜各个面型的轮廓曲线。利用TracePro软件对所设计的聚光系统进行光线追迹模拟,结果表明:在聚光比为725的情况下,聚焦光斑最大照度仅为太阳照度的2300倍,是点聚焦情况下的1/10左右,系统的径长比为0.3,接收角为0.72°。系统设计实现了结构紧凑,聚光性能高的设计目标,为高倍聚光光伏系统的小型化,简单化提供了一种有效的解决途径。     

Molecules relevant for organic photovoltaics: a range-separated density functional study

Accurate determination of both fundamental and optical gap is necessary for designing molecules relevant for organic photovoltaics. Here, we study how range-separated density functionals reproduce frontier orbital energies, HOMO (highest occupied molecular orbital)–LUMO (lowest unoccupied molecular orbital) gaps, and optical gaps for molecules relevant for organic photovoltaics. In this study, we consider 12 different range-separated density functional for computing HOMO energy, HOMO–LUMO gap, and optical gap which are compared with available experimental and reported GW values. We found that the reproduction of desired photovoltaic properties primarily depend on range separation parameter. Moreover, the tested functionals are comparable with OT-BNL functional.     

Synthesis and Characterization of a Thiophene Copolymer for Photovoltaic Application

A soluble thiophene copolymer having polar and non polar side groups was synthesized and its photovoltaics performance was investigated. The synthesized copolymer was characterized using Nuclear Magnetic Resonance (NMR) and optical spectroscopy. Dye sensitized solar cells were fabricated using this copolymer as sensitizer. An open-circuit voltage of 0.50V, a short-circuit current density of 1.195 mA/cm² and an overall power conversion efficiency of 0.3% were measured.