Tunable Rectification in 2D Porphyrinic Metal–Organic Framework Nanosheets Molecular Heterojunctions

Abstract As functional electrical devices advance, new strategies for regulating electrical properties are essential for achieving diverse electrical performance. In this study, molecular heterojunction rectifiers are constructed by connecting porphyrinic 2D metal–organic framework (2D MOF) nanoshee...

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Main Authors: Bing Huang, Xiaoyu Wang, Chaoguang He, Yongkang Zhang, Pan Qi, Ying Wang, Tong Li, Huixia Fu, Hui Wei, Cunlan Guo
Format: Article
Language:English
Published: Wiley-VCH 2025-06-01
Series:Advanced Electronic Materials
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Online Access:https://doi.org/10.1002/aelm.202400773
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author Bing Huang
Xiaoyu Wang
Chaoguang He
Yongkang Zhang
Pan Qi
Ying Wang
Tong Li
Huixia Fu
Hui Wei
Cunlan Guo
author_facet Bing Huang
Xiaoyu Wang
Chaoguang He
Yongkang Zhang
Pan Qi
Ying Wang
Tong Li
Huixia Fu
Hui Wei
Cunlan Guo
author_sort Bing Huang
collection DOAJ
description Abstract As functional electrical devices advance, new strategies for regulating electrical properties are essential for achieving diverse electrical performance. In this study, molecular heterojunction rectifiers are constructed by connecting porphyrinic 2D metal–organic framework (2D MOF) nanosheets and oligophenylene thiols self‐assembled monolayers (OPT SAMs) within metal electrodes. The rectification characteristics can be tuned by the molecular length of OPT and the coordinated metal atom in the center of 2D MOFs. Specifically, a rectification ratio of more than 1.67 orders of magnitude is achieved in the heterojunction composed of 2D Zn‐TCPP MOF nanosheet (TCCP, tetrakis(4‐carboxyphenyl) porphyrin) and OPT3 SAM. Combining Kelvin probe force microscopy measurements and first‐principles calculations of the 2D MOF nanosheets, it elucidates that the rectification variations come from the adjustment of energy level alignment at OPT SAMs//2D MOF interface, leading to asymmetric charge transport with the voltage polarities. This strategy can be further extended to Cu‐MOF nanosheets, which also exhibit rectification behaviors when placed on OPT2 SAMs. This work provides a universal and flexible strategy for regulating the electrical behaviors of MOFs without the need for specific design and synthesis, paving the way for the development of MOF‐based functional electronic devices.
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issn 2199-160X
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spelling doaj-art-a0805438abe2432a8a10dd4df8039f542025-08-20T03:19:28ZengWiley-VCHAdvanced Electronic Materials2199-160X2025-06-01118n/an/a10.1002/aelm.202400773Tunable Rectification in 2D Porphyrinic Metal–Organic Framework Nanosheets Molecular HeterojunctionsBing Huang0Xiaoyu Wang1Chaoguang He2Yongkang Zhang3Pan Qi4Ying Wang5Tong Li6Huixia Fu7Hui Wei8Cunlan Guo9College of Chemistry and Molecular Sciences Wuhan University Wuhan Hubei 430072 ChinaDepartment of Biomedical Engineering College of Engineering and Applied Sciences Nanjing National Laboratory of Microstructures Jiangsu Key Laboratory of Artificial Functional Materials Nanjing University Nanjing Jiangsu 210023 ChinaCenter of Quantum Materials and Devices College of Physics Chongqing University Chongqing 401331 ChinaCollege of Chemistry and Molecular Sciences Wuhan University Wuhan Hubei 430072 ChinaCollege of Chemistry and Molecular Sciences Wuhan University Wuhan Hubei 430072 ChinaCollege of Chemistry and Molecular Sciences Wuhan University Wuhan Hubei 430072 ChinaDepartment of Biomedical Engineering College of Engineering and Applied Sciences Nanjing National Laboratory of Microstructures Jiangsu Key Laboratory of Artificial Functional Materials Nanjing University Nanjing Jiangsu 210023 ChinaCenter of Quantum Materials and Devices College of Physics Chongqing University Chongqing 401331 ChinaDepartment of Biomedical Engineering College of Engineering and Applied Sciences Nanjing National Laboratory of Microstructures Jiangsu Key Laboratory of Artificial Functional Materials Nanjing University Nanjing Jiangsu 210023 ChinaCollege of Chemistry and Molecular Sciences Wuhan University Wuhan Hubei 430072 ChinaAbstract As functional electrical devices advance, new strategies for regulating electrical properties are essential for achieving diverse electrical performance. In this study, molecular heterojunction rectifiers are constructed by connecting porphyrinic 2D metal–organic framework (2D MOF) nanosheets and oligophenylene thiols self‐assembled monolayers (OPT SAMs) within metal electrodes. The rectification characteristics can be tuned by the molecular length of OPT and the coordinated metal atom in the center of 2D MOFs. Specifically, a rectification ratio of more than 1.67 orders of magnitude is achieved in the heterojunction composed of 2D Zn‐TCPP MOF nanosheet (TCCP, tetrakis(4‐carboxyphenyl) porphyrin) and OPT3 SAM. Combining Kelvin probe force microscopy measurements and first‐principles calculations of the 2D MOF nanosheets, it elucidates that the rectification variations come from the adjustment of energy level alignment at OPT SAMs//2D MOF interface, leading to asymmetric charge transport with the voltage polarities. This strategy can be further extended to Cu‐MOF nanosheets, which also exhibit rectification behaviors when placed on OPT2 SAMs. This work provides a universal and flexible strategy for regulating the electrical behaviors of MOFs without the need for specific design and synthesis, paving the way for the development of MOF‐based functional electronic devices.https://doi.org/10.1002/aelm.202400773electrical regulation strategymetal–organic frameworksmolecular heterojunctionsrectificationself‐assembled monolayers
spellingShingle Bing Huang
Xiaoyu Wang
Chaoguang He
Yongkang Zhang
Pan Qi
Ying Wang
Tong Li
Huixia Fu
Hui Wei
Cunlan Guo
Tunable Rectification in 2D Porphyrinic Metal–Organic Framework Nanosheets Molecular Heterojunctions
Advanced Electronic Materials
electrical regulation strategy
metal–organic frameworks
molecular heterojunctions
rectification
self‐assembled monolayers
title Tunable Rectification in 2D Porphyrinic Metal–Organic Framework Nanosheets Molecular Heterojunctions
title_full Tunable Rectification in 2D Porphyrinic Metal–Organic Framework Nanosheets Molecular Heterojunctions
title_fullStr Tunable Rectification in 2D Porphyrinic Metal–Organic Framework Nanosheets Molecular Heterojunctions
title_full_unstemmed Tunable Rectification in 2D Porphyrinic Metal–Organic Framework Nanosheets Molecular Heterojunctions
title_short Tunable Rectification in 2D Porphyrinic Metal–Organic Framework Nanosheets Molecular Heterojunctions
title_sort tunable rectification in 2d porphyrinic metal organic framework nanosheets molecular heterojunctions
topic electrical regulation strategy
metal–organic frameworks
molecular heterojunctions
rectification
self‐assembled monolayers
url https://doi.org/10.1002/aelm.202400773
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AT yongkangzhang tunablerectificationin2dporphyrinicmetalorganicframeworknanosheetsmolecularheterojunctions
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