• Journal of Photoscience
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• 제7권2호
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• pp.67-71
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• 2000

A quantum-chemical investigation on the conformations and electronic properties of trans(diphenyl-diheterocyclic) ethenes(t-PHEs) as building block for fully $\pi$-conjuated polymer are performed in order to display the effects of heterocyclic ring substitution. Structures for the molecules, t-PHEs were fully optimized by using semiempirical AM1, PM3 methods, and ab initio HF methods, with 6-31G basic set. The potential energy curves with respect to the change of single are obtained by using ab initio HF/6-31G basic set. The curves are not similar shapes in the molecules with respect to heterocyclic rings. It is shown that the steric repulsion interactions between phenyl ring and heterocyclic ring are subjected to different type with the respect to each heterocyclic ring. Electronic properties of the molecules were molecules were obtained by applying the optimized structures and selected geometries to the extended Huckel method. To investigate the change of HOMO-LUMO gap with respedt to the torsion angle, we select the optimized structures. By using the results, the dependency of conjugation for the energy gaps is analyzed. For t-PHE the energy gap increase up to 0.52 eV compared with its planar structure. In the cases of t-PHE and t-PHE, the energy gap increase by 1.29 and 1.15 eV, respectively, compared with its planar structure.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.11.2-11.2
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• 2011

Polymer based organic photovoltaics have attracted a great deal of attention due to the potential cost-effectiveness of light-weight and flexible solar cells. However, most BHJ polymer solar cells are not thermally stable as subsequent exposure to heat drives further development of the morphology towards a state of macrophase separation in the micrometer scale. Here we would like to show three different approaches for developing new electroactive polymers to improve the thermal stability of the BHJ solar cells, which is a critical problem for the commercialization of these solar cells. For one of the examples, we report a new series of functionalized polythiophene (PT-x) copolymers for use in solution processed organic photovoltaics (OPVs). PT-x copolymers were synthesized from two different monomers, where the ratio of the monomers was carefully controlled to achieve a UV photo-crosslinkable layer while leaving the ${\pi}-{\pi}$ stacking feature of conjugated polymers unchanged. The crosslinking stabilizes PT-x/PCBM blend morphology preventing the macro phase separation between two components, which lead to OPVs with remarkably enhanced thermal stability. The drastic improvement in thermal stabilities is further characterized by microscopy as well as grazing incidence X-ray scattering (GIXS). In the second part of talk, we will discuss the use of block copolymers as active materials for WOLEDs in which phosphorescent emitter isolation can be achieved. We have exploited the use of triarylamine (TPA) oxadiazole (OXA) diblock copolymers (TPA-b-OXA), which have been used as host materials due to their high triplet energy and charge-transport properties enabling a balance of holes and electrons. Organization of phosphorescent domains in TPA-b-OXA block copolymers is demonstrated to yield dual emission for white electroluminescence. Our approach minimizes energy transfer between two colored species by site isolation through morphology control, allowing higher loading concentration of red emitters with improved device performance. Furthermore, by varying the molecular weight of TPA-b-OXA and the ratio of blue to red emitters, we have investigated the effect of domain spacing on the electroluminescence spectrum and device performance.

• 한국정보디스플레이학회:학술대회논문집
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• 한국정보디스플레이학회 2007년도 7th International Meeting on Information Display 제7권1호
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• pp.667-670
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• 2007

A new series of highly bright and efficient poly(pphenylenevinylene) s (PPV)s based on polyhedral oligomeric silsesquioxanes (POSSs) was synthesized via the Gilch polymerization method. The three POSScontaining PPVs are as follows: POSS05- PPV(containing 5 mol % POSS-appended PPV units), POSS25-PPV(containing 25 mol % POSS-appended PPV units), and POSS100-PPV(containing 100 mol % POSS-appended PPV units; this is the first ${\pi}-conjugated$ polymer composed of 100 mol % POSSsappended repeating units). The POSS-containing PPVs exhibit higher glass transition temperatures $(64-77^{\circ}C)$ than that of MEH-PPV $(58^{\circ}C)$, indicating that electroluminescence (EL) devices fabricated with these polymers should have good thermal stabilities. Light-emitting diodes (LEDs) with the configuration of ITO/PEDOT:PSS/polymer/Ca/Al were fabricated using the novel POSS-containing PPVs. Surprisingly, the luminescence efficiency (0.48 cd/A at $10540\;cd/m^2$) of the binary blend consisting 5 wt % of POSS25-PPV and 95 wt % of MEH-PPV was found to be enhanced by a factor of 6.4 with a maximum brightness of $11010cd/m^2$ (at 14.3 V).

• Bulletin of the Korean Chemical Society
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• 제23권2호
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• pp.330-336
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• 2002

A quantum-chemical investigation on the conformations and electronic properties of bis[2-{2-methoxy-4,6-di(t-butyl)phenyl}ethenyl]benzenes (MBPBs) as building block for ${\pi}$-conjugate polymer are performed in order to display the effects of t-butyl and methoxy group substitution and of kink(ortho and meta) linkage. The conjugation length of the polymers can be controlled by substituents and kink linkages of backbone. Structures for the molecules, o-, m-, and p-MBPBs as well as unsubstituted o-, m-, and p-DSBs were fully optimized by using semiempirical AM1, PM3 methods, and ab initio HF method with 3-21G(d) basis set. The potential energy curves with respect to the change of single torsion angle are obtained by using semiempirical methods and ab initio HF/3-21G(d) basis set. The curves are similar shape in the molecules with respect to the position of vinylene groups. It is shown that the conformations of the molecules are compromised between the steric repulsion interaction and the degree of the conjugation. Electronic properties of the molecules were obtained by applying the optimized structures and geometries to the ZINDO/S method. ZINDO/S analysis performed on the geometries obtained by AM1 method and HF/3-21G(d) level is reported. The absorption wavelength on the geometries obtained by AM1 method is much longer than that by HF/3-21G(d) level. The absorption wavelength of MBPBs are red shifted with comparison to that of corresponding DSBs in the same torsion angle because of electron donating substituents. The absorption wavelength of isomers with kink(orth and meta) linkage is shorter than that of para linkage.

• Bulletin of the Korean Chemical Society
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• 제32권2호
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• pp.417-423
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• 2011

A series of new quinoxaline-based thiophene copolymers (PQx2T, PQx4T, and PQx6T) was synthesized via Yamamoto and Stille coupling reactions. The $M_ws$ of PQx2T, PQx4T, and PQx6T were found to be 20,000, 12,000, and 29,000, with polydispersity indices of 2.0, 1.2, and 1.1, respectively. The UV-visible absorption spectra of the polymers showed two distinct absorption peaks in the ranges 350 - 460 nm and 560 - 600 nm, which arose from the ${\pi}-{\pi}^*$ transition of oligothiophene units and intramolecular charge transfer (ICT) between a quinoxaline acceptor and thiophene donor. The HOMO levels of the polymer ranged from -5.37 to -5.17 eV and the LUMO levels ranged from -3.67 to -3.45 eV. The electrochemical bandgaps of PQx2T, PQx4T, and PQx6T were 1.70, 1.71, and 1.72 eV, respectively, thus yielding low bandgap behavior. PQx2T, PQx4T, and PQx6T had open circuit voltages of 0.58, 0.42, and 0.47 V, and short circuit current densities of 2.9, 5.29 and 9.05 mA/$cm^2$, respectively, when $PC_{71}BM$ was used as an acceptor. For the solar cells with PQx2T-PQx6T:$PC_{71}BM$ (1:3) blends, an increase in performance was observed in going from PQx2T to PQx6T. The power conversion efficiencies of PQx2T, PQx4T, and PQx6T devices were found to be 0.69%, 0.73%, and 1.80% under AM 1.5 G (100 mW/$cm^2$) illumination.