有机太阳能电池热失效机制及三元共混提升其热稳定性研究进展

有机太阳能电池(Organic solar cells, OSCs)作为一种新兴高效太阳能电池,近年来得到飞速发展.目前OSCs的光电转换效率(Powerconversionefficiency,PCE)已经达到19%以上,初见商业化应用曙光.但其稳定性方面尚未发展成熟,尤其在制备和工作过程中电池器件需要经历高温考验,电池的热稳定性要求高.三元共混策略是在传统的二元OSCs活性层中引入第三组分,利用第三组分调控分子间的相互作用,在实现高效光电转换效率的同时有效提高器件热稳定性,展现出了极大的应用潜力.本综述首先从器件热衰减过程出发,总结了OSCs热衰减过程中包括:热致活性层形貌变化、各层材料之间的互扩散行为以及界面老化等相关机制.在此基础上,重点介绍了三元策略在提高OSCs热稳定性方面的应用进展和作用机制.最后,对三元策略在OSCs中的应用发展进行总结并展望,指出第三组分的针对性选择以及作用机制解析是三元OSCs面临的关键问题和挑战.     

Molecular Suction Pads: Self‐Assembled Monolayers of Subphthalocyaninatoboron Complexes on Gold

Subphthalocyaninatoboron complexes with six long‐chain alkylthio substituents in their periphery are applicable for the formation of self‐assembled monolayers (SAMs) on gold. Such films are prepared from solution with the axially chlorido‐substituted derivatives and characterised by near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy, X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The results are in accord with the formation of SAMs assembled by the chemisorption of both covalently bound thiolate‐type as well as coordinatively bound thioether units. The adsorbate molecules adopt an essentially flat adsorption geometry on the substrate, resembling a suction pad on a surface.     

二磺酸掺杂高热稳定性导电聚苯胺的合成及性能

以有机二磺酸作为掺杂剂合成了具有高热稳定性的二磺酸掺杂导电聚苯胺。研究了反应时间、温度、酸/苯胺摩尔比等因素对产率、产物的导电率与分子量的影响。利用微波加热的方法测试有机二磺酸掺杂聚苯胺的热稳定性能，结果表明：有机二磺酸掺杂的导电聚苯胺在微波场中升温速率快，并且具有良好的反复升温性能。     

Tetrachlorinated Tetraazaperopyrenes (TAPPs): Highly Fluorescent Dyes and Semiconductors for Air‐Stable Organic n‐Channel Transistors and Complementary Circuits

A range of 2,9‐perfluoroalkyl‐substituted tetraazaperopyrene (TAPP) derivatives ( 1 – 5 ) was synthesised by reacting 4,9‐diamino‐3,10‐perylenequinone diimine (DPDI) with the corresponding carboxylic acid chloride or anhydride in the presence of a base. The reaction of compounds 1 – 4 with dichloroisocyanuric acid (DIC) in concentrated sulphuric acid resulted in the fourfold substitution of the tetraazaperopyrene core, yielding the 2,9‐bisperfluoroalkyl‐4,7,11,14‐tetrachloro‐1,3,8,10‐tetraazaperopyrenes 6 – 9 , respectively. The optical and electrochemical data demonstrate the drastic influence of the core substitution on the properties. All compounds are highly luminescent (fluorescence quantum yields of up to Φ=0.8). The LUMO energies of the tetrachlorinated TAPP derivatives (determined by cyclic voltammetry and computed by DFT calulations) were found to be below ?4 eV. In the course of this work the performance of TAPP derivatives in organic thin‐film transistors (TFTs) was investigated, and their n‐channel characteristics with field‐effect mobilities of up to 0.14 cm² V^?1 s^?1 and an on/off current ratio of >10⁶ were confirmed. Long‐term stabilities of 3–4 months under ambient conditions of the devices were established. Complementary inverters and ring oscillators with n‐channel TFTs based on compound 8 and p‐channel TFTs based on dinaphtho‐[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (DNTT) were fabricated on a glass substrate.     

过碳酰胺分子合成条件优化、晶体结构及其热稳定性

采用四因素、三水平的方法研究了过碳酰胺分子合成中物料比、反应温度、反应时间、稳定剂的种类对合成收率的影响,获得了合成的最佳工艺条件。 在最佳合成条件下,测得过碳酰胺的产率可达到99%,活性氧含量最高可达到17.5%。 通过热分析方法研究了过碳酰胺分子热稳定性。 研究表明,温度超过65 ℃过碳酰胺含量和含氧量均迅速下降。 利用X射线单晶衍射仪测定了其晶体结构,使用Diamond软件解析出过碳酰胺分子的三维空间超分子结构及其氢键的连接方式。     

Solution‐Based Direct Growth of Organic Crystals on an Active Channel Region for Printable Bottom‐Contact Organic Field‐Effect Transistors

The growth and self‐organization of organic crystals between a source (S) and drain (D) electrode by a method based on the use of a micropipette and isothermal evaporation of the solvent in a two‐liquid system led to the formation of organic‐crystal transistors (see polarized optical micrograph). The method is similar to ink‐jet printing and should be suitable for the fabrication of low‐cost and mass‐producible printed electronic devices.

     

Synthesis,Structure and High Thermal Stability of a Novel Three‐dimensional Zinc(II) Complex with an Unsymmetrical Rigid‐flexible Ligand

A novel metal‐organic framework, [Zn(C₁₀H₈O₅)]_n ( 1 ) (C₁₀H₈O₅ = 2‐(4‐carboxylatophenoxy)propionate), was synthesized and characterized by elemental analysis, IR spectroscopy, X‐ray crystallography and thermogravimetric analysis. The crystal structure study reveals that each zinc atom is coordinated by four oxygen atoms from four different ligands to obtain a distorted tetrahedron. The rigid carboxyl group bridges two adjacent zinc atoms to form a dimer of eight‐membered rings, whereas the flexible carboxyl group bridges two adjacent dimers to form 1D chains along the a axis. Two adjacent 1D chains are interconnected by the ligands to produce 2D layers. These layers are further stabilized by intermolecular hydrogen bonds to construct a 3D framework showing high thermal stability (445 °C).     

Effect of Inorganic Components on Thermal Stability of Methylsiloxane-Based Inorganic/Orgnaic Hybrids

The thermal decomposition behavior of methylsiloxane-based inorganic/organic hybrids containing an inorganic component derived from metal alkoxides such as Si(OCH₃)₄, Al(O^sC₄H₉)₃, Ti(OⁱC₃H₇)₄ and Nb(OC₂H₅)₅ was investigated by means of thermogravimetric and differential thermal analysis (TG-DTA), Fourier transform infrared (FT-IR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. The decomposition temperature of methyl groups in methylsiloxane-based inorganic/organic hybrids containing an inorganic component derived from metal alkoxides was higher than that in the methylsiloxane-based inorganic/organic hybrid prepared from only CH₃Si(OC₂H₅)₃. In particular, when incorporating Nb and Ti inorganic components, methyl groups in methylsiloxane-based inorganic/organic hybrids decomposed at about 100 and 200^∘C higher temperatures, respectively, than those in the methylsiloxane-based inorganic/organic hybrid prepared from only CH₃Si(OC₂H₅)₃. The incorporation of an inorganic component other than siloxane into methylsiloxane-based inorganic/organic hybrids was found to thermally stabilize the methyl groups of methylsiloxane networks.     

纳米ZnO对天然橡胶交联反应和热稳定性的影响

纳米氧化锌;纳米ZnO对天然橡胶交联反应和热稳定性的影响     

Synthesis and Properties of Semiconducting Bispyrrolothiophenes for Organic Field‐Effect Transistors

A series of new highly soluble bispyrrolothiophenes were synthesized from vinyl azides by using transition‐metal‐catalyzed C?H‐bond functionalization. In addition to modifying the substituents present on the end‐pyrrolothiophene moieties, the arene linker in between the two units was also varied. The solution‐state properties and field‐effect‐transistor (FET) electrical behavior of these bispyrrolothiophenes was compared. Our investigations identified that the optical properties and oxidation potential of our compounds were dominated by the pyrrolothiophene unit with a λ_max value of approximately 400 nm and oxidation at approximately 1 V. FET devices constructed with thin films of these bispyrrolothiophenes were also fabricated by means of thin‐film solution processing. One of these compounds, a bispyrrolothiophene linked with benzothiodiazole, exhibits a mobility of approximately 0.3 cm² V^?1 s^?1 and the I_on/I_off value is greater than 10⁶.     

Molecular and Electronic‐Structure Basis of the Ambipolar Behavior of Naphthalimide–Terthiophene Derivatives: Implementation in Organic Field‐Effect Transistors

A new family of naphthalimide‐fused thienopyrazine derivatives for ambipolar charge transport in organic field‐effect transistors is presented. Their electronic and molecular structures were elucidated through optical and vibrational spectroscopy aided by DFT calculations. The results indicate that these compounds have completely planar molecular skeletons which promote good film crystallinity and low reorganization energies for both electron and hole transport. Their performance in organic field‐effect transistors is compared with twisted and planar naphthaleneamidine monoimide‐fused terthiophenes in order to understand the origin of ambipolarity in this new series of molecular semiconductors.     

Synthesis,Structures, and Properties of Fused Thiophenes for Organic Field‐Effect Transistors

A series of fused thiophenes composed of fused α‐oligothiophene units as building blocks, end‐capped with either styrene or 1‐pentyl‐4‐vinylbenzene groups, has been synthesized through Stille coupling reactions. The compounds have been fully characterized by means of ¹H NMR spectrometry, high‐resolution mass spectrometry, and elemental analysis. The molecules present a trans–trans configuration between their double bonds, which has been verified and confirmed by Fourier‐transform infrared spectroscopy and single‐crystal X‐ray diffraction analysis. The X‐ray crystal structures showed π–π overlap and sulfur–sulfur interactions between the adjacent molecules. The decomposition temperatures were all found to be above 300 °C, indicating that compounds of this series possess excellent thermal stability. The fact that no phase transition occurs at low temperature indicates that they should be well‐suited for application in devices. Moreover, they possess low HOMO energy levels, based on cyclic voltammetry measurements, and suitable energy gaps, as determined from their thin‐film UV/Vis spectra. Thin‐film X‐ray diffraction analysis and atomic force microscopy revealed high crystallinity on supporting substrates. In addition, as the substrate temperature has a significant influence on the morphology and the degree of crystallinity, the device performance could be optimized by varying the substrate temperature. These materials were found to exhibit optimal field‐effect performance, with a mobility of 0.17 cm² V^?1 s^?1 and an on/off ratio of 10⁵, at a substrate temperature of 70 °C.     

Vacuum Surface Science Meets Heterogeneous Catalysis: Dehydrogenation of a Liquid Organic Hydrogen Carrier in the Liquid State

Ultrahigh vacuum (UHV) surface science techniques are used to study the heterogeneous catalytic dehydrogenation of a liquid organic hydrogen carrier in its liquid state close to the conditions of real catalysis. For this purpose, perhydrocarbazole (PH), otherwise volatile under UHV, is covalently linked as functional group to an imidazolium cation, forming a non‐volatile ionic liquid (IL). The catalysed dehydrogenation of the PH unit as a function of temperature is investigated for a Pt foil covered by a macroscopically thick PH‐IL film and for Pd particles suspended in the PH‐IL film, and for PH‐IL on Au as inert support. X‐ray photoelectron spectroscopy and thermal desorption spectroscopy allows us to follow in situ the catalysed transition of perhydrocarbazole to carbazole at technical reaction temperatures. The data demonstrate the crucial role of the Pt and Pd catalysts in order to shift the dehydrogenation temperature below the critical temperature of thermal decomposition.     

The chemistry and thermal stability of HfTaO/Si interface by x‐ray photoelectron spectroscopy

The chemistry and thermal stability of HfTaO/Si interface as a function of annealing temperature have been investigated by x‐ray photoelectron spectroscopy. For the as‐deposited sample, the formation of Hf‐silicate bond is observed on Hf 4f core‐level spectra, which contributes to bulk HfO₂ and SiO₂. Besides, the suboxide of tantalum (Ta⁺¹) is formed at the interface at room temperature because of oxygen‐deficient conditions. HfSi₂, Hf_xSi_yO_4, and HfO₂ coexists in interfacial region at 850 °C, meanwhile, an evidence for transforming from the Ta¹⁺ to tantalum oxide (Ta⁵⁺) is verified. The peaks of Hf–O–Si and Hf–O have disappeared, only one peak of Hf silicide remained after the annealing at 950 °C. A stable SiO₂ phase in HfTaO/Si is formed under different annealing conditions. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of Nd-doping on the Thermal Stability and Pore-structure of Al2O3 Membranes

Unsupported Nd-doped Al2O3 membranes have been prepared with a sol-gel treatnt by using aiuminium isopropoxide and Nd(NO3)3 as the main raw materials. The properties of Nd-doped Al2O3 membranes were characterized by XRD, DTA-TG, IR and N2 adsorption. The effects of Nd-doping on the phase composition, thermal stability as well as applications of porestructure of Nd-doped Al2O3 membranes at high temperature were discussed. The results show that Nd-doping can raise the transition temperature rom γ-Al203 to α-Al2O3, enhance the thermal stability of Al2O3 membranes, and evidently improve the pore-structural parameters of Al2O3 membranes applied at higher temperatures.