염료감응 태양전지용 새로운 아연(II)함유 포르피린 유도체의 합성 및 특성 연구 Novel Extended π-conjugated Zn(II)-porphyrin Derivatives for Dye Sensitized Solar Cell Based on Quasi-solid-state Polymeric Electrolytes: Synthesis and Characterization원문보기
본 연구에서는 합성이 용이하고 광전변환율이 우수한 새로운 아연(II)함유 포르피린 염료를 합성하고자 하였으며, 보다 구체적으로는 포르피린에 다양한 치환기를 도입하여 인접한 포르피린 염료간의 거리를 멀리함으로서 여기상태 및 산화된 포르피린 염료가 여기전자 혹은 분리된 자유전자와의 재결합을 통해 ...
본 연구에서는 합성이 용이하고 광전변환율이 우수한 새로운 아연(II)함유 포르피린 염료를 합성하고자 하였으며, 보다 구체적으로는 포르피린에 다양한 치환기를 도입하여 인접한 포르피린 염료간의 거리를 멀리함으로서 여기상태 및 산화된 포르피린 염료가 여기전자 혹은 분리된 자유전자와의 재결합을 통해 바닥상태로 전환됨을 방지하고 또한 여기상태의 포르피린으로부터 전해질로 전자가 재결합하는 것을 방지하는 새로운 구조의 포르피린 염료를 합성하고자 하였다. 포르피린의 컨쥬게이션 길이를 늘림으로써 흡수영역을 적색이동 시키고자 스틸벤 그룹을 도입하였으며 효과적인 전자주입을 위하여 -CN 치환기를 스틸벤 그룹에 치환시켰다. 또한 입체장애가 있는 1세대 아릴-에테르 덴드론 혹은 트리페닐아민을 도입함으로써 인접한 여기상태의 포르피린 염료간의 재결합을 방지하고자 하였다. 마지막으로 카르복시산을 도입하여 티타늄 산화물에 염료가 화학적으로 흡착될 수 있도록 하였다. 합성한 포르피린은 1H-NMR, FT-IR, Mass 등을 이용하여 구조를 분석하였고 흡수, 여기 및 가시광선 영역에서의 발광을 측정하여 광학적 특성을 규명하였으며 C-V 스펙트럼을 통해 포르피린 염료들의 전기화학적 특성을 규명하였다. 합성한 포르피린 염료와 고체상태 전해질을 사용하여 염료감응 태양전지 소자를 제조하였을 때 트리페닐 아민과 -CN 그룹을 함께 도입된 포르피린 염료의 에너지 변환 효율이 3.48%로 가장 높음을 확인할 수 있었다.
본 연구에서는 합성이 용이하고 광전변환율이 우수한 새로운 아연(II)함유 포르피린 염료를 합성하고자 하였으며, 보다 구체적으로는 포르피린에 다양한 치환기를 도입하여 인접한 포르피린 염료간의 거리를 멀리함으로서 여기상태 및 산화된 포르피린 염료가 여기전자 혹은 분리된 자유전자와의 재결합을 통해 바닥상태로 전환됨을 방지하고 또한 여기상태의 포르피린으로부터 전해질로 전자가 재결합하는 것을 방지하는 새로운 구조의 포르피린 염료를 합성하고자 하였다. 포르피린의 컨쥬게이션 길이를 늘림으로써 흡수영역을 적색이동 시키고자 스틸벤 그룹을 도입하였으며 효과적인 전자주입을 위하여 -CN 치환기를 스틸벤 그룹에 치환시켰다. 또한 입체장애가 있는 1세대 아릴-에테르 덴드론 혹은 트리페닐아민을 도입함으로써 인접한 여기상태의 포르피린 염료간의 재결합을 방지하고자 하였다. 마지막으로 카르복시산을 도입하여 티타늄 산화물에 염료가 화학적으로 흡착될 수 있도록 하였다. 합성한 포르피린은 1H-NMR, FT-IR, Mass 등을 이용하여 구조를 분석하였고 흡수, 여기 및 가시광선 영역에서의 발광을 측정하여 광학적 특성을 규명하였으며 C-V 스펙트럼을 통해 포르피린 염료들의 전기화학적 특성을 규명하였다. 합성한 포르피린 염료와 고체상태 전해질을 사용하여 염료감응 태양전지 소자를 제조하였을 때 트리페닐 아민과 -CN 그룹을 함께 도입된 포르피린 염료의 에너지 변환 효율이 3.48%로 가장 높음을 확인할 수 있었다.
The use of porphyrins as light harvesters or photosensitizers on DSSCs is particularly attractive, due to their primary role in photosynthesis and the relative ease with which a variety of covalent or noncovalent porphyrin arrays can be developed. The attachment of a large porphyrin array to a nanoc...
The use of porphyrins as light harvesters or photosensitizers on DSSCs is particularly attractive, due to their primary role in photosynthesis and the relative ease with which a variety of covalent or noncovalent porphyrin arrays can be developed. The attachment of a large porphyrin array to a nanocrystalline wide-band gap semiconductor surface provides a way to dramatically increase the surface dye concentration and the light energy conversion efficiency of the device. Various porphyrins have been used as the photosensitizer of the DSSCs, the most common being the free-base and zinc derivatives of the meso-substituted porphyrin. In a recent report, the power conversion efficiency was optimized for tetrakis(4-carboxyphenyl)porphyrins)-based DSSCs and the addition of a coadsorbent. Very recently, Grätzel group also reported that the power conversion efficiency was improved due to the optimization of Zinc metalloporphyrins-based DSSCs and the addition of a coadsorbent (Voc = 0.566 V, Jsc = 13.5 mA/cm2, and η = 5.2 %). To date, this is the best-reported value for a porphyrin photoelectrochemical cell (PEC), and was achieved using a chenodeoxycholic acid (DCA) as a coadsorbent. However, Wamser et al. have also reported a solid state based DSSC, which uses aminophenyltricarboxyphenylporphyrin dye (TC3APP) with an aniline gel-based electrolyte system, giving a conversion efficiency of 0.8%. The reason why porphyrin derivatives are less efficient sensitizer dyes, compared with those of ruthenium complex based dyes in DSSCs, probably arise from an increased probability of exciton annihilation. Tachibana et al. suggested that at high porphyrin coverage, dipole/dipole interactions would allow rapid migration of the excited state between neighboring porphyrins, increasing the probability of exciton annihilation, whereas, the low emission dipole of the ruthenium bipyridyl complex metal-to-ligand charge transfer (MLCT) state would prevent such a migration. In this study, to reduce the probability of exciton annihilation from rapid migration of the excited state between neighboring porphyrin dyes, we report the synthesis and photo conversion efficiency of novel extended π-conjugated Zn(II)-porphyrins derivatives, such as 1st aryl ether typed dendron substituted Zn(II)-porphyrin derivatives [G-1]ZnP-CN and triphenylamine substituted ([TPA]ZnP or [TPA]ZnP-CN). The chemical structures of these Zn(II)-porphyrin derivatives were characterized by 1H-NMR, FT-IR, UV-vis absorption, EI-mass, and MALDI-TOF mass spectrocopies and they have been used to fabricate dye-sensitized solar cells devices based on solid polymeric electrolytes as a dye sensitizer. Device performance was evaluated by comparing with that of the standard Ru(II) complex dye. The [TPA]Zn-P-CN1 sensitized solar cell demonstrates a short circuit photocurrent density of 13.7 mA/cm2, an open-circuit voltage of 0.53 V, and a fill factor of 0.48. This corresponds to an overall conversion efficiency of 3.48 %, making it the most efficient porphyrin-sensitized solar cell based on solid polymeric electrolyte reported to date.
The use of porphyrins as light harvesters or photosensitizers on DSSCs is particularly attractive, due to their primary role in photosynthesis and the relative ease with which a variety of covalent or noncovalent porphyrin arrays can be developed. The attachment of a large porphyrin array to a nanocrystalline wide-band gap semiconductor surface provides a way to dramatically increase the surface dye concentration and the light energy conversion efficiency of the device. Various porphyrins have been used as the photosensitizer of the DSSCs, the most common being the free-base and zinc derivatives of the meso-substituted porphyrin. In a recent report, the power conversion efficiency was optimized for tetrakis(4-carboxyphenyl)porphyrins)-based DSSCs and the addition of a coadsorbent. Very recently, Grätzel group also reported that the power conversion efficiency was improved due to the optimization of Zinc metalloporphyrins-based DSSCs and the addition of a coadsorbent (Voc = 0.566 V, Jsc = 13.5 mA/cm2, and η = 5.2 %). To date, this is the best-reported value for a porphyrin photoelectrochemical cell (PEC), and was achieved using a chenodeoxycholic acid (DCA) as a coadsorbent. However, Wamser et al. have also reported a solid state based DSSC, which uses aminophenyltricarboxyphenylporphyrin dye (TC3APP) with an aniline gel-based electrolyte system, giving a conversion efficiency of 0.8%. The reason why porphyrin derivatives are less efficient sensitizer dyes, compared with those of ruthenium complex based dyes in DSSCs, probably arise from an increased probability of exciton annihilation. Tachibana et al. suggested that at high porphyrin coverage, dipole/dipole interactions would allow rapid migration of the excited state between neighboring porphyrins, increasing the probability of exciton annihilation, whereas, the low emission dipole of the ruthenium bipyridyl complex metal-to-ligand charge transfer (MLCT) state would prevent such a migration. In this study, to reduce the probability of exciton annihilation from rapid migration of the excited state between neighboring porphyrin dyes, we report the synthesis and photo conversion efficiency of novel extended π-conjugated Zn(II)-porphyrins derivatives, such as 1st aryl ether typed dendron substituted Zn(II)-porphyrin derivatives [G-1]ZnP-CN and triphenylamine substituted ([TPA]ZnP or [TPA]ZnP-CN). The chemical structures of these Zn(II)-porphyrin derivatives were characterized by 1H-NMR, FT-IR, UV-vis absorption, EI-mass, and MALDI-TOF mass spectrocopies and they have been used to fabricate dye-sensitized solar cells devices based on solid polymeric electrolytes as a dye sensitizer. Device performance was evaluated by comparing with that of the standard Ru(II) complex dye. The [TPA]Zn-P-CN1 sensitized solar cell demonstrates a short circuit photocurrent density of 13.7 mA/cm2, an open-circuit voltage of 0.53 V, and a fill factor of 0.48. This corresponds to an overall conversion efficiency of 3.48 %, making it the most efficient porphyrin-sensitized solar cell based on solid polymeric electrolyte reported to date.
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