Molecular Orientation of -PO3H2 and -COOH Functionalized Dyes on TiO2, Al2O3, ZrO2, and ITO: A Comparative Study.
Molecular Orientation of -PO3H2 and -COOH Functionalized Dyes on TiO2, Al2O3, ZrO2, and ITO: A Comparative Study.
复制标题
-PO3H2 和 -COOH 功能化染料在 TiO2、Al2O3、ZrO2 和 ITO 上的分子取向：比较研究。
DOI：
10.1021/acs.jpcc.2c08632
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
ScottSaavedra,S
中科院分区：
文献类型：
--
作者：
Pattadar,Dhruba;Zheng,Lianqing;Robb,AlexJ;Beery,Drake;Yang,Wei;Hanson,Kenneth;ScottSaavedra,S
用有机单分子膜修饰金属氧化物（MOx）被广泛用于调整有机电子器件和染料敏化太阳能电池中的界面性质。修饰的效果通常通过在模型单分子膜上进行实验来评估|MOx接口，其中“惰性”MOx（例如，Al 2 O3）用作“活性”MOx（例如，TiO 2）。这些研究中的一个基本假设是，惰性和活性单层|MOx结构类似。在此对这一假设进行了检验。采用紫外-可见衰减全反射光谱法，研究了4，4 ′-（蒽-9，10-二基）双（4，1-亚苯基）二膦酸（A1 P）在氧化铟锡（ITO）、二氧化钛（TiO 2）、氧化锆（ZrO 2）和氧化铝（Al 2 O3）表面的吸附行为.当MOx衬底的表面粗糙度和AlP薄膜的表面覆盖率（Γ）一定时，AlP薄膜的取向是相同的。4，4 ′-（蒽-9，10-二基）双（4，1-亚苯基）二羧酸（A1 C）吸附在同一组MOx底物上。ITO上的Al和Al P的取向是相同的，这可能是由于两种膜的高且近似相等的Γ导致的分子间相互作用。同样，在相同的表面粗糙度下，比较在TiO_2和Al_2 O_3上的相同Γ的Al_1C膜，取向是相同的。MD模拟ofA 1CandA 1 Pon TiO 2产生几乎相同的倾斜角分布，支持实验结果。这项研究提供了第一个实验验证的假设，|无论金属氧化物衬底的性质如何，MOx结构都是相同的。
Modifying metal oxides (MOx) with organic monolayers is widely employed to tailor interfacial properties in organic electronic devices and dye-sensitized solar cells. The effects of modification are frequently assessed by performing experiments on model monolayer|MOxinterfaces, where an “inert” MOx(e.g., Al2O3) is used as a control for an “active” MOx(e.g., TiO2). An underlying assumption in these studies is that the inert and active monolayer|MOxstructures are similar. This assumption was examined here. Using UV–vis attenuated total reflection spectroscopy, we measured the mean tilt angle of 4,4′-(anthracene-9,10-diyl)bis(4,1-phenylene)diphosphonic acid (A1P) adsorbed on indium tin oxide (ITO), TiO2, ZrO2, and Al2O3. When the surface roughness of the MOxsubstrate and the surface coverage (Γ) of theA1Pfilm were constant, the orientation ofA1Pwas the same. 4,4′-(Anthracene-9,10-diyl)bis(4,1-phenylene)dicarboxylic acid (A1C) was adsorbed on the same set of MOxsubstrates. The orientation ofA1CandA1Pon ITO was the same, which is likely due to the intermolecular interactions resulting from the high and approximately equal Γ of both films. ComparingA1Cfilms at equal Γ on TiO2and Al2O3with equal surface roughness, again, the orientation was the same. MD simulations ofA1CandA1Pon TiO2produced nearly identical tilt angle distributions, supporting the experimental findings. This study provides the first experimental validation of the assumption that the monolayer|MOxstructure is the same regardless of the nature of the metal oxide substrate.