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本田 充紀; 柳田 真利*; Han, L.*; 宮野 健次郎*
Journal of Chemical Physics, 141(17), p.174709_1 - 174709_7, 2014/11
被引用回数：8 パーセンタイル：29.76(Chemistry, Physical)The interface between Ru(tcterpy)(NCS)
TBA
[black dye (BD); tcterpy = 4,4',4''-tricarboxy-2,2':6',2''-terpyridine, TBA = tetrabutylammonium cation] and nanocrystalline TiO, as found in dye-sensitized solar cells, is investigated by soft-X-ray synchrotron radiation and compared with the adsorption structure of 
-Ru(Hdcbpy)(NCS)TBA (N719; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) on TiO to elucidate the relationship between the adsorption mode of BD and the photocurrent with and without coadsorbed indoline dye D131. The depth profile is characterized with X-ray photoelectron spectroscopy and S 
-edge X-ray absorption fine structure using synchrotron radiation. Both datasets indicate that one of the isothiocyanate groups of BD interacts with TiO via its S atom when the dye is adsorbed from a single-component solution. In contrast, the interaction is slightly suppressed when D131 is coadsorbed, indicated by the fact that the presence of D131 changes the adsorption mode of BD. Based upon these results, the number of BD dye molecules interacting with the substrate is shown to decrease by 10% when D131 is coadsorbed, and the dissociation is shown to be related to the short-circuit photocurrent in the 600-800 nm region. The design of a procedure to promote the preferential adsorption of D131 therefore leads to an improvement of the short-circuit current and conversion efficiency.
本田 充紀; 柳田 真利*; Han, L.*; 宮野 健次郎*
e-Journal of Surface Science and Nanotechnology (Internet), 12, p.63 - 67, 2014/02
Quantifying the coadsorption of dye molecules on nanoporous TiO is difficult because of the complex adsorption structure between the dye and TiO surface. D131 dye absorbs strongly in the ultraviolet region and is a common co-sensitizer for dye-sensitized solar cells. In this study, we showed that Cl-terminated D131 dye coadsorbed with a Ru complex on nanoporous TiO can be used as a labeling compound to quantify coadsorption systems by X-ray photoelectron spectroscopy (XPS). Cl-terminated D131 alone and Cl-terminated D131 and N719 coadsorbed on nanoporous TiO were measured with XPS. The Cl atoms were quantified by the peak intensity ratio of the Cl 1s and Ti 2p peaks. In the Cl-terminated D131 + N719 coadsorption system, the amount of Cl-terminated D131 dye adsorbed decreased by about 44% for the 1:1 mixture. Our technique could also be used to quantify other dyes in co-sensitizer systems, such as black dye and N3 dye.
表面における混合色素(N719/D131)の吸着状態本田 充紀; 柳田 真利*; Han, L.*; 宮野 健次郎*
no journal, ,
色素増感太陽電池(DSCs)は、導電透明酸化電極、光吸収の役割を担う増感色素が吸着した酸化チタン(TiO)の多孔質半導体層、ヨウ素系電解質、対極から構成され次世代太陽電池として期待されている。しかしDSCsの光電変換効率は11-12%とSi系太陽電池の半分程度にどまっており効率向上には発電機構解明が望まれている。DSCsで用いられるTiOは粒径が数十nmのナノポーラス構造でありその表面に約1nmの色素が吸着しているが、色素吸着状態は未だ解明されていない。今回ナノポーラスTiO表面上でのN719色素吸着状態を軟X線放射光によるX線構造解析により詳細に検討した。N719単体およびN719+D131混合試料について入射角
=90
で測定したときのS K-edge NEXAFS spectraについて、N719の中心のRu金属に配位している-NCSのSのK吸収端を詳細に比較検討した。その結果、N719単体時には二つの共鳴吸収ピークを2474eV(ピークA)および2476eV(ピークB)に観測した。ピークAは
(S=C)にピークBは
(S-C)に帰属される。またピークCは9eV高いエネルギーの2483eVに観測された。これは酸化したS原子に帰属されることより、NCSがTiO基板と相互作用していることを示唆する。一方、N719にD131を混合した場合には、ピークCに大きな変化を確認した。これはD131を混合することでNCSとTiOの相互作用が解消することを意味し、共吸着色素吸着構造を詳細に解明した。
本田 充紀; 柳田 真利*; Han, L.*; 宮野 健次郎*
no journal, ,
We are developing for new XAFS system under operand condition in soft X-ray regions. Recently, we performed X-ray measurments and we have get S K-edge NEXAFS spectra under operand conditions. In this study, one of the result from this system, we performed X-ray measurements to elucidate the adsorption mode of Ru complex (N719) molecules on nanoporous TiO under operand conditions. Two conditions, near-edge X-ray absorption fine structure spectroscopy, were employed in order to obtain depth profile information about the substrate. In both cases, we found that the S K-edge of Ru complex (N719) strongly interact with TiO via S atoms when the Ru complex is adsorbed from a single-component solution. In contrast, S-substrate interaction is strongly suppressed when D131 is coadsorbed with N719, indicating that the presence of D131 changes the adsorption mode of N719. Based on this finding, we successfully obtained the XAFS spectra under operand conditions in soft X-ray regions.
