We investigate terahertz radiation(T-rays) from a pentacene organic diode at room temperature. The quantum chemistry calculation for frequency-related Huang–Rhys factor of pentacene is also carried out. The results demonstrate that the T-rays can come from a bending vibration of pentacene skeleton after the energy of pentacene exciton transferring to the vibrational excited state via electron–phonon coupling. Frequency and natural bond orbital analytics of pentacene and its derivatives are performed in order to explain the result and develop new materials to get higher emission. This work provides a new way to produce T-rays with a simple device at room temperature.
Temperature-dependent aggregation is a key property for some donor polymers to realize favorable bulk-heterojunction(BHJ)morphologies and high-efficiency(>10%) polymer solar cells.Previous studies find that an important structural feature that enables such temperature-dependent aggregation property is the 2nd position branched alkyl chains sitting between two thiophene units.In this report,we demonstrate that an optimal extent of fluorination on the polymer backbone is a second essential structural feature that enables the strong temperature-dependent aggregation property.We compare the properties of three structurally similar polymers with 0,2 or 4 fluorine substitutions in each repeating unit through an in-depth morphological study.We show that the non-fluorinated polymer does not aggregate in solution(0.02 mg mL^(-1) in chlorobenzene) at room temperature,which results in poor polymer crystallinity and extremely large polymer domains.On the other hand,the polymer with four fluorine atoms in each repeating unit exhibits an excessively strong tendency to aggregate,which makes it difficult to process and causes a large domain.Only the polymer with two fluorine atoms in each repeating unit exhibits a suitable extent of temperature-dependent aggregation property.As a result,its blend film achieves a favorable morphology and high power conversion efficiency.This provides another key design rationale for developing donor polymers with suitable temperature-dependent aggregation properties and thus high performance.
Guofang YangZhengke LiKui JiangJie ZhangJianya ChenGuangye ZhangFei HuangWei MaHe Yan
Organic light-emitting diodes(OLEDs) have been extensively studied since the first efficient device based on small molecular luminescent materials was reported by Tang. Organic electroluminescent material, one of the centerpieces of OLEDs, has been the focus of studies by many material scientists. To obtain high luminosity and to keep material costs low, a few remarkable design concepts have been developed. Aggregation-induced emission(AIE) materials were invented to overcome the common fluorescence-quenching problem, and cross-dipole stacking of fluorescent molecules was shown to be an effective method to get high solid-state luminescence. To exceed the limit of internal quantum efficiency of conventional fluorescent materials, phosphorescent materials were successfully applied in highly efficient electroluminescent devices. Most recently, delayed fluorescent materials via reverse-intersystem crossing(RISC) from triplet to singlet and the "hot exciton" materials based on hybridized local and charge-transfer(HLCT) states were developed to be a new generation of low-cost luminescent materials as efficient as phosphorescent materials. In terms of the device-fabrication process, solution-processible small molecular luminescent materials possess the advantages of high purity(vs. polymers) and low procession cost(vs. vacuum deposition), which are garnering them increasing attention. Herein, we review the progress of the development of small-molecule luminescent materials with different design concepts and features, and also briefly examine future development tendencies of luminescent materials.
A new silole monomer with two 4-(N,N-dimethylamino)phenyl substitutions on silicon atom as designed and synthesized.Three copolymers PF-N-HPS1,PF-N-HPS10 and PF-N-HPS20 were then obtained by copolymerizations of 2,7-fluorene derivatives with the silole monomer at feed ratios of 1%,10%,and 20%.Their UV-vis absorption,electrochemical,photoluminescent,and electroluminescent (EL) properties were investigated.PF-N-HPS possessed HOMO levels of 5.25-5.58 eV,and showed green emissions.Using PF-N-HPS as the emissive layer,three different polymer light-emitting diodes were fabricated as device A with ITO/PEDOT/PF-N-HPS/Al,device B with ITO/PEDOT/PF-N-HPS/Ba/Al,and device C with ITO/PEDOT/PF-N-HPS/TPBI/Ba/Al.For the device A,PF-N-HPS only showed very low EL efficiency of 0.06-0.33 cd/A,indicating that the Al cathode could not inject electron efficiently to the emissive polymers containing the 4-(N,N-dimethylamino)phenyl groups.For the device B,low work function Ba supplied better electron injections,and the EL efficiency could be improved to 0.85-1.44 cd/A.TPBI with a deep HOMO level of 6.2 eV could enhance electron transport and hole blocking.Thus modified recombinations and largely elevated EL efficiency of 4.56-7.96 cd/A were achieved for the device C.The separation of the emissive layer and metal cathode with the TPBI layer may also suppress exciton quenching at the cathode interface.
LIU ZhiTianHU SuJunZHANG LinHuaCHEN JunWuPENG JunBiaoCAO Yong
Two new conjugated copolymers,PBDT-T6-TTF and PBDT-T12-TTF,were derived from a novel 4-fluorobenzoyl thienothiophene(TTF).In addition,two types of benzodithiophene(BDT)units with 2,3-dihexylthienyl(T6)and 2,3-didodecylthienyl(T12)substituents,respectively,were successfully synthesized.The effect of the dual two-dimensional(2D)substitutions of the building blocks upon the optoelectronic properties of the polymers was investigated.Generally,the two polymers exhibited good solubility and broad absorption,showing similar optical band gaps of^1.53 e V.However,PBDT-T6-TTF with its shorter alkyl chain length possessed a larger extinction coefficient in thin solid film.The highest occupied molecular orbital(HOMO)level of PBDT-T6-TTF was located at–5.38 e V while that of PBDT-T12-TTF was at–5.51 e V.In space charge-limitedcurrent(SCLC)measurement,PBDT-T6-TTF and PBDT-T12-TTF displayed respective hole mobilities of 3.0×10–4 and1.6×10–5 cm2 V1 s1.In polymer solar cells,PBDT-T6-TTF and PBDT-T12-TTF showed respective power conversion efficiencies(PCEs)of 2.86%and 1.67%.When 1,8-diiodooctane(DIO)was used as the solvent additive,the PCE of PBDT-T6-TTF was remarkably elevated to 4.85%,but the use of DIO for the PBDT-T12-TTF-blend film resulted in a lower PCE of 0.91%.Atomic force microscopy(AFM)indicated that the superior efficiency of PBDT-T6-TTF with 3%DIO(v/v)should be related to the better continuous phase separation of the blend film.Nevertheless,the morphology of the PBDT-T12-TTF deteriorated when the 3%DIO(v/v)was added.Our results suggest that the alkyl-chain length on the 2D BDT units play an important role in determining the optoelectronic properties of dual 2D BDT-TT-based polymers.
Zhulin LiuJiangman SunYongxiang ZhuPeng LiuLianjie ZhangJunwu ChenFei HuangYong Cao
Compositing gold nanoparticles into conjugated molecules have been developed to be one of the most important approaches to increase stability, since degradation of conjugated materials is now one of the biggest bottle-necks to be conquered before industrialization application. Big-size colloidal gold nanoparticles with strong surface plasma resonance are designed to composite with conjugated molecules, in order to realize effective fluorescence enhancement and stabilization. The uniform composition film of hydrophilic colloidal gold nanoparticles (particle diameter of 30 nm) and hydrophobic carbazole functionalized fluorene trimers has been obtained by direct mixing of their aqueous and THF solutions, which is determined by AFM. By the comparison of composition based on fluorene trimers with similar structures, we have found that peripheral carbazole group and molecular size of fluorene trimers play an important role in the balance of incompatible solubility, which is regarded as increasing solubility of fluorene trimers in mixed solvent, connecting AuNP and peripheral carbazole groups, and restraining aggregate of gold nanoparticle. This allows facile hydrophilic gold nanoparticle to disperse uniformly in hydrophobic-conjugated host. Our investigations show that fluorescence intensity of composition film is enhanced by 4 folds, and heat treatment (200°C for 4h) for the composition film does not induce the degradation of conjugated backbone without the appearance of low-energy emission band, demonstrating the prominent potency of gold nanoparticles in enhanced fluorescence and stability of conjugated molecules and polymers.
Polycyclic aromatics (PCAs) possess excellent photoelectric properties, but the construction of such compounds has been a quite challenging subject of study, mainly due to very low solubility. Herein we report a precursor synthesis strategy for polycyclic aromatic conjugated polymers. A soluble precursor polymer, that containing fusible "double U-shaped aromatic"(DUA) and perylenetetracarboxydiimide (PDI) units, was firstly synthesized by Suzuki coupling. The stereo aromatic units in polymer backbone were found to be converted into polycyclic aromatic units, i.e. hexa-peri-hexabenzocoronene (HBC), by chemical or electrochemical oxidation, which resulted in a formation of insoluble polycyclic aromatic conjugated polymers. The electrochemical oxidations that occurred at the interface of electrode and solution exhibited higher cyclization reactivity and leads to the formation of high quality films on the electrode surface. Characterization by Raman and UV-visible (UV-Vis) spectroscopy validated the successful formation of this HBC structure. Some potential applications of such thin films are being explored, and here we focus on the characteristics of supercapacitors based on their excellent electrochemical properties.
Zhenhua ZhangWeitao MaBiao XuXuehong ZhouCong WangZengqi XieLinlin LiuYuguang Ma
