十六氟酞菁鋅與酞菁鋅之超快載子動力學

Ultrafast Carrier Dynamics of Hexadecafluorinated Zinc Phthalocyanine (F16ZnPc) and Zinc Phthalocyanine (ZnPc)

劉維勳(Wei-Syun Liou)

指導教授 ： 安惠榮

國立交通大學/電機學院/光電工程系所/碩士(2014年)

https://doi.org/10.6842/NCTU.2014.00335

摘要

Phthalocyanines (Pc) are superior material, because it superior properties including ultrafast response, thermal and chemical stability, and flexible processing so that Pcs have been widely investigated for use in a various optoelectronic devices, such as thin film transistors. Pc dyes are two-dimensional aromatic molecules with an inner ring consisting of 18 π-electrons. In Pc molecules, various kinds of metal atoms can be coordinated to the center of rings and their chemical and electronic properties may be tuned through the choice of metal center. Standard Metallophthalocyanine (MPcs) are p-type organic semiconductor, and we can alter the molecular orbital structure drastically, and leading to n-type MPcs by addition of electron and remove the functional groups, particularly fluorine. Zinc Pc (ZnPc) and Hexadecafluorinated zinc (F16ZnPc) is an interesting material for photovoltaic and photoconductivity applications due to their high absorption coefficient in a wide spectral range of solar radiation and high energy conversion efficiency and photochemical stability. Using the absorption spectroscopy and femtosecond time-resolved pump-probe spectroscopy, we investigated the absorption properties and excited states relaxation dynamics attributed to the effects of morphology, including rod size and molecular interaction of ZnPc and F16ZnPc films. Transient differential transmittance signals show polarization dependence and excitation intensity dependence of the photoexcited ZnPc and F16ZnPc. The nano-structure of ZnPc and F16ZnPc show anisotripic relaxation of excitons for s- and p-polarized probe beams. We also employ ultrafast optical spectroscopy at different wavelengths to understand the inter-band decay in the excited state of F16ZnPc. The relaxation process is slower in the F16ZnPc than in the ZnPc due to the weak exciton coupling (longer stack distance) and steric obstruction created by the peripherally substituent (F-atoms) in F16ZnPc.

關鍵字

超快載子動力學 ； 十六氟酞菁鋅 ； 酞菁鋅

並列摘要

Phthalocyanines (Pc) are superior material, because it superior properties including ultrafast response, thermal and chemical stability, and flexible processing so that Pcs have been widely investigated for use in a various optoelectronic devices, such as thin film transistors. Pc dyes are two-dimensional aromatic molecules with an inner ring consisting of 18 π-electrons. In Pc molecules, various kinds of metal atoms can be coordinated to the center of rings and their chemical and electronic properties may be tuned through the choice of metal center. Standard Metallophthalocyanine (MPcs) are p-type organic semiconductor, and we can alter the molecular orbital structure drastically, and leading to n-type MPcs by addition of electron and remove the functional groups, particularly fluorine. Zinc Pc (ZnPc) and Hexadecafluorinated zinc (F16ZnPc) is an interesting material for photovoltaic and photoconductivity applications due to their high absorption coefficient in a wide spectral range of solar radiation and high energy conversion efficiency and photochemical stability. Using the absorption spectroscopy and femtosecond time-resolved pump-probe spectroscopy, we investigated the absorption properties and excited states relaxation dynamics attributed to the effects of morphology, including rod size and molecular interaction of ZnPc and F16ZnPc films. Transient differential transmittance signals show polarization dependence and excitation intensity dependence of the photoexcited ZnPc and F16ZnPc. The nano-structure of ZnPc and F16ZnPc show anisotripic relaxation of excitons for s- and p-polarized probe beams. We also employ ultrafast optical spectroscopy at different wavelengths to understand the inter-band decay in the excited state of F16ZnPc. The relaxation process is slower in the F16ZnPc than in the ZnPc due to the weak exciton coupling (longer stack distance) and steric obstruction created by the peripherally substituent (F-atoms) in F16ZnPc.

並列關鍵字

ultrafast carrier dynamics ； Zinc phthalocyanine ； Hexadecafluorinated Zinc Phthalocyanine

參考文獻

[2] D. Hohnholz, S. Steinbrecher, and M. Hanack, "Applications of phthalocyanines in organic light emitting devices," Journal of Molecular Structure, vol. 521, pp. 231-237, 2000.

[4] E. Orti, J. Bredas, and C. Clarisse, "Electronic structure of phthalocyanines: theoretical investigation of the optical properties of phthalocyanine monomers, dimers, and crystals," The Journal of chemical physics, vol. 92, pp. 1228-1235, 1990.

[5] H. Tajalli, J. Jiang, J. Murray, N. Armstrong, A. Schmidt, M. Chandross, et al., "Spectra of third‐order optical nonlinear susceptibilities of epitaxial chloro‐indium‐phthalocyanines," Applied physics letters, vol. 67, pp. 1639-1641, 1995.

[7] A. v. Braun and J. Tcherniac, "Über die Produkte der Einwirkung von Acetanhydrid auf Phthalamid," Berichte der deutschen chemischen Gesellschaft, vol. 40, pp. 2709-2714, 1907.

[8] H. de Diesbach and E. von der Weid, "Quelques sels complexes des o‐dinitriles avec le cuivre et la pyridine," Helvetica Chimica Acta, vol. 10, pp. 886-888, 1927.