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Surface Dissociation Effect on Phosphonic Acid Self-Assembled Monolayer Formation on ZnO Nanowires.

ABSTRACT: Understanding the formation process of self-assembled monolayers (SAMs) of organophosphonic acids on ZnO surfaces is essential to designing their various applications, including solar cells, heterogeneous catalysts, and molecular sensors. Here, we report the significant effect of surface dissociation on SAM formation of organophosphonic acids on single-crystalline ZnO nanowire surfaces using infrared spectroscopy. When employing the most conventional solvent-methanol (relative permittivity ε_r = 32.6), the production of undesired byproducts (layered zinc compounds) on the surface was identified by infrared spectral data and microscopy. On the other hand, a well-defined SAM structure with a tridentate coordination of phosphonic acids on the surface was confirmed when employing toluene (ε_r = 2.379) or tert-butyl alcohol (ε_r = 11.22-11.50). The observation of layered zinc compounds as byproducts highlights that the degree of Zn²⁺ dissociation from the ZnO solid surface into a solvent significantly affects the surface coordination of phosphonic acids during the SAM formation process. Although the ZnO nanowire surface (m-plane) is hydrophilic, the present results suggest that a weaker solvent polarity is preferred to form well-defined phosphonic acid SAMs on ZnO nanowire surfaces without detrimental surface byproducts.

SUBMITTER: Nakamura K

PROVIDER: S-EPMC8756575 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

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Surface Dissociation Effect on Phosphonic Acid Self-Assembled Monolayer Formation on ZnO Nanowires.

Nakamura Kentaro K Takahashi Tsunaki T Hosomi Takuro T Yamaguchi Yu Y Tanaka Wataru W Liu Jiangyang J Kanai Masaki M Nagashima Kazuki K Yanagida Takeshi T

ACS omega 20211227 1

Understanding the formation process of self-assembled monolayers (SAMs) of organophosphonic acids on ZnO surfaces is essential to designing their various applications, including solar cells, heterogeneous catalysts, and molecular sensors. Here, we report the significant effect of surface dissociation on SAM formation of organophosphonic acids on single-crystalline ZnO nanowire surfaces using infrared spectroscopy. When employing the most conventional solvent-methanol (relative permittivity ε<sub ...[more]

PMID: 35036808

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Project description:Metal halide perovskites have attracted tremendous attention due to their excellent electronic properties. Recent advancements in device performance and stability of perovskite solar cells (PSCs) have been achieved with the application of self-assembled monolayers (SAMs), serving as stand-alone hole transport layers in the p-i-n architecture. Specifically, phosphonic acid SAMs, directly functionalizing indium-tin oxide (ITO), are presently adopted for highly efficient devices. Despite their successes, so far, little is known about the surface coverage of SAMs on ITO used in PSCs application, which can affect the device performance, as non-covered areas can result in shunting or low open-circuit voltage. In this study, we investigate the surface coverage of SAMs on ITO and observe that the SAM of MeO-2PACz ([2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid) inhomogeneously covers the ITO substrate. Instead, when adopting an intermediate layer of NiO between ITO and the SAM, the homogeneity, and hence the surface coverage of the SAM, improve. In this work, NiO is processed by plasma-assisted atomic layer deposition (ALD) with Ni(MeCp)2 as the precursor and O2 plasma as the co-reactant. Specifically, the presence of ALD NiO leads to a homogeneous distribution of SAM molecules on the metal oxide area, accompanied by a high shunt resistance in the devices with respect to those with SAM directly processed on ITO. At the same time, the SAM is key to the improvement of the open-circuit voltage of NiO + MeO-2PACz devices compared to those with NiO alone. Thus, the combination of NiO and SAM results in a narrower distribution of device performance reaching a more than 20% efficient champion device. The enhancement of SAM coverage in the presence of NiO is corroborated by several characterization techniques including advanced imaging by transmission electron microscopy (TEM), elemental composition quantification by Rutherford backscattering spectrometry (RBS), and conductive atomic force microscopy (c-AFM) mapping. We believe this finding will further promote the usage of phosphonic acid based SAM molecules in perovskite PV.

Dataset Information

Surface Dissociation Effect on Phosphonic Acid Self-Assembled Monolayer Formation on ZnO Nanowires.

Publications

Surface Dissociation Effect on Phosphonic Acid Self-Assembled Monolayer Formation on ZnO Nanowires.

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