Here we demonstrate a simple and effective method of fabricating polymeric scattering substrate for flexible organic light-emitting diodes (OLEDs) that require no costly patterning, etching, or molding processes, aspects that are desirable for the commercialization of large-scale lighting panels. Systematic study of the influences of relative index of refraction, particle size, and doping concentration on transmittance and haze of transparent colorless polyimide (cPI) films was carried out. It was found that the reduction of transmittance and haze of the doped films decreases along with the decrease of the difference of refractive index between the particles and polymer matrix, and it could be compensated by the increase of particle size or doping concentration.
Flexible surface-enhanced Raman scattering (SERS) sensors have attracted great attention as a portable and low-cost device for chemical and bio-detection. However, flexible SERS sensors tend to suffer low signal spatial homogeneity due to the uneven distribution of active plasmonic nanostructures (hot spots) and quick degradation of their sensitivity due to low adhesion of hot spots and flexible substrates during fast sampling. Herein, a large-area (20 × 20 cm 2 ) polyimide (PI)-based SERS sensor is exploited for trace detection with high signal homogeneity and stability. The SERS sensor is constructed from PI through in situ growth of silver and gold core−shell nanoparticles (Ag@Au NPs) based on chemical reduction and galvanic replacement processes. Benefiting from the abundant carboxyl groups on the surfacecleaved PI, densely and uniformly distributed Ag@Au NPs are successfully prepared on the film under ambient conditions. The high Raman enhancement factor (EF) (up to 1.07 × 10 7 ) and detection capability with low nanomolar (10 −9 M) detection limits are obtained for this flexible SERS sensor. The uniform Raman signals in the random region show good signal homogeneity with a low variation of 8.7%. Moreover, the flexible SERS sensor exhibited superior efficiency and durability after storage for 30 days even after 500 cycles of mechanical stimuli (bending or torsion). The residue of pesticide thiram (tetramethylthiuram disulfide, TMTD) has been rapidly traced by direct sampling from the apple surface, and a sensitivity of 10 ng/cm 2 for TMTD was achieved. These findings show that the PI-based SERS sensor is a very strong candidate for broad and simple utilization of flexible SERS for both laboratory and commercial applications in chemical and biomolecule detections.
Donor–acceptor alternating copolymers with chlorine atoms on the backbone are synthesized via a straightforward Stille polycondensation. Thiophene and chlorine‐substituted 2,3‐diphenylquinoxaline are chosen as the donor and acceptor moieties, respectively. Compared with the corresponding non‐substituted and fluorine‐substituted analogues, which are also synthesized for systematical studies, the chlorine‐bearing copolymer exhibits the deepest lowest unoccupied molecular orbital (LUMO). The highest occupied molecular orbital (HOMO) level of the chlorine‐bearing copolymer can be modified by applying different donor moieties. Additionally, these chlorine‐bearing copolymers show low self‐absorption and large Stokes Shift.
Due to the development of dynamic flexible organic light‐emitting diode displays, colorless polyimides (CPI) as the supporting or protecting optical films, are facing significant challenges due to the requirements of optical, mechanical, thermal, and chemical properties. Typical CPIs are derived from TFDB (2,2‐bis(trifluoro‐methyl)‐4,4′‐diaminobiphenyl)/6FDA (4,4′‐(hexafluoroisopropylidene)diphthalic anhydride), which still need to be improved in both dimensional stability and optical performance. In this communication, a strong electron acceptor group, the sulfoxide bond, is first introduced into the TFDB block of CPI chains. Based on this introduction, the distribution of the electron cloud in the polymer chain is reconstructed under the strongly pulling electron effect, and the spatial conformation of the polymer chain is also affected by the rigid and twisted sulfoxide group. The influences on CPI's optical properties, especially the refractive index and the retardation, are studied and discussed in detail by experimental results and theoretical calculations. It is shown that the CPI with the sulfoxide group exhibits higher optical transparency, lower yellow index, phase retardation and coefficient of thermal expansion, which is an ideal material for CPI optical films.
A new series of colorless polyimides (CPIs) with outstanding thermal properties and mechanical properties were fabricated by the copolymerization of a novel dianhydride and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with 2,2′-bistrifluoromethyl benzidine (TFDB). The novel dianhydride, 10-oxo-9-phenyl-9-(trifluoromethyl)-9,10-dihydroanthracene-2,3,6,7-tetraacid dianhydride (3FPODA), possessed a rigid semi-alicyclic structure, –CF3 and phenyl side groups, and an active carbonyl group. Benefitting from the special structure of 3FPODA, the glass transition temperatures (Tg) of the new CPIs improved from 330 °C to 377 °C, the coefficient of thermal expansion (CTE) decreased from 46 ppm/K to 24 ppm/K, and the tensile strength (TS), tensile modulus (TM), and elongation at break (EB) increased from 84 MPa to 136 MPa, 3.2 GPa to 4.4 GPa, and 2.94% to 4.13% with the increasing amount of 3FPODA, respectively. Moreover, the active carbonyl group of the 3FPODA could enhance the CPI’s adhesive properties. These results render the new dianhydride 3FPODA an ideal candidate monomer for the fabrication of high-performance CPIs.
An interface stabilizer based on alkylation-functionalized fullerene derivatives, [6, 6]-Phenyl-C61-butyric acid (3,5-bis(octyloxy)phenyl)methyl ester (PCB-C8oc), was successfully synthesized and applied for the active layer of Organic Photovoltaics (OPVs). The PCB-C8oc can replace part of the phenyl-C61-buty-ric acid methyl ester (PCBM) and be distributed on the interface of poly(3-hexylthiophene) (P3HT) and PCBM to form P3HT/PCBM/PCB-C8oc ternary blends, leading to thermally stable and efficient organic photovoltaics. The octyl groups of PCB-C8oc exhibit intermolecular interaction with the hexyl groups of P3HT, and the fullerene unit of PCB-C8oc are in tight contact with PCBM. The dual functions of PCB-C8oc will inhibit the phase separation between electron donor and acceptor, thereby improving the stability of devices under long-time thermal annealing at high temperature. When doped with 10 wt % PCB-C8oc, the power conversion efficiency (PCE) of the P3HT system decreased from 3.54% to 2.88% after 48 h of thermal treatment at 150 °C, whereas the PCE of the reference device without PCB-C8oc dramatically dropped from 3.53% to 0.73%. When doping 10 or 20 wt % PCB-C8oc, the unannealed P3HT/PCBM/PCB-C8oc device achieved a higher PCE than the P3HT/PCBM device without any annealing following the same fabricating condition. For the PTB7/PCBM-based devices, after adding only 5 wt % PCB-C8oc, the OPVs also exhibited thermally stable morphology and better device performances. All these results demonstrate that the utilization of alkyl interchain interactions is an effective and practical strategy to control morphological evolution.
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