Unveiling Electronic Properties in Metal-Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks

Mingchao Wang; Marco Ballabio; Mao Wang; Hung Hsuan Lin; Bishnu P. Biswal; Xiaocang Han; Silvia Paasch; Eike Brunner; Pan Liu; Mingwei Chen; Mischa Bonn; Thomas Heine; Shengqiang Zhou; Enrique Cánovas; Renhao Dong; Xinliang Feng

doi:10.1021/jacs.9b07644

Unveiling Electronic Properties in Metal-Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks

Mingchao Wang, Marco Ballabio, Mao Wang, Hung Hsuan Lin, Bishnu P. Biswal, Xiaocang Han, Silvia Paasch, Eike Brunner, Pan Liu, Mingwei Chen, Mischa Bonn, Thomas Heine, Shengqiang Zhou, Enrique Cánovas, Renhao Dong, Xinliang Feng

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

154 Citations (Scopus)

Abstract

π-Conjugated two-dimensional covalent organic frameworks (2D COFs) are emerging as a novel class of electroactive materials for (opto)electronic and chemiresistive sensing applications. However, understanding the intricate interplay between chemistry, structure, and conductivity in π-conjugated 2D COFs remains elusive. Here, we report a detailed characterization for the electronic properties of two novel samples consisting of Zn- and Cu-phthalocyanine-based pyrazine-linked 2D COFs. These 2D COFs are synthesized by condensation of metal-phthalocyanine (M = Zn and Cu) and pyrene derivatives. The obtained polycrystalline-layered COFs are p-type semiconductors both with a band gap of ∼1.2 eV. A record device-relevant mobility up to ∼5 cm²/(V s) is resolved in the dc limit, which represents a lower threshold induced by charge carrier localization at crystalline grain boundaries. Hall effect measurements (dc limit) and terahertz (THz) spectroscopy (ac limit) in combination with density functional theory (DFT) calculations demonstrate that varying metal center from Cu to Zn in the phthalocyanine moiety has a negligible effect in the conductivity (∼5 × 10^-7 S/cm), charge carrier density (∼10¹² cm^-3), charge carrier scattering rate (∼3 × 10¹³ s^-1), and effective mass (∼2.3m₀) of majority carriers (holes). Notably, charge carrier transport is found to be anisotropic, with hole mobilities being practically null in-plane and finite out-of-plane for these 2D COFs.

Original language	English
Pages (from-to)	16810-16816
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	141
Issue number	42
DOIs	https://doi.org/10.1021/jacs.9b07644
Publication status	Published - 2019 Oct 23

Bibliographical note

Funding Information:
We thank financial support from EU Graphene Flagship, ERC Consolidator Grant (T2DCP), ERC Starting Grant (FC2DMOF, No. 852909), Coordination Networks: Building Blocks for Functional Systems (SPP 1928, COORNET) as well as the German Science Council, Center of Advancing Electronics Dresden, EXC1056, (cfaed), and OR 349/1. We acknowledge the Dresden Center for Nanoanalysis (DCN) at TUD; Dr. Philipp Schlender, Dr. Konrad Schneider (Leibniz Institute for Polymer Research, IPF, Dresden), Dr. Tilo Lübken, and Mr. Friedrich Schwotzer for the use of facilities. We also appreciate Mr. Ji Ma, Dr. Haixia Zhong, and Ms. Yu Zhang (UvA) for the MS, SEM, and XPS analysis, respectively. We thank Mr. Chi Xu (HZDR), Dr. Chongqing Yang, and Dr. Zhongquan Liao (IKTS) for the helpful discussions. Prof. T. Heine and Hung-Hsuan Lin acknowledge the Centre for Information Services and High-Performance Computing (ZIH) in Dresden, Germany, for the provided computational resources.

Publisher Copyright:
© 2019 American Chemical Society.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.9b07644

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Wang, M., Ballabio, M., Wang, M., Lin, H. H., Biswal, B. P., Han, X., Paasch, S., Brunner, E., Liu, P., Chen, M., Bonn, M., Heine, T., Zhou, S., Cánovas, E., Dong, R., & Feng, X. (2019). Unveiling Electronic Properties in Metal-Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks. Journal of the American Chemical Society, 141(42), 16810-16816. https://doi.org/10.1021/jacs.9b07644

@article{0bfe77898a5647628ed73c24fcc4a73a,

title = "Unveiling Electronic Properties in Metal-Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks",

abstract = "π-Conjugated two-dimensional covalent organic frameworks (2D COFs) are emerging as a novel class of electroactive materials for (opto)electronic and chemiresistive sensing applications. However, understanding the intricate interplay between chemistry, structure, and conductivity in π-conjugated 2D COFs remains elusive. Here, we report a detailed characterization for the electronic properties of two novel samples consisting of Zn- and Cu-phthalocyanine-based pyrazine-linked 2D COFs. These 2D COFs are synthesized by condensation of metal-phthalocyanine (M = Zn and Cu) and pyrene derivatives. The obtained polycrystalline-layered COFs are p-type semiconductors both with a band gap of ∼1.2 eV. A record device-relevant mobility up to ∼5 cm2/(V s) is resolved in the dc limit, which represents a lower threshold induced by charge carrier localization at crystalline grain boundaries. Hall effect measurements (dc limit) and terahertz (THz) spectroscopy (ac limit) in combination with density functional theory (DFT) calculations demonstrate that varying metal center from Cu to Zn in the phthalocyanine moiety has a negligible effect in the conductivity (∼5 × 10-7 S/cm), charge carrier density (∼1012 cm-3), charge carrier scattering rate (∼3 × 1013 s-1), and effective mass (∼2.3m0) of majority carriers (holes). Notably, charge carrier transport is found to be anisotropic, with hole mobilities being practically null in-plane and finite out-of-plane for these 2D COFs.",

author = "Mingchao Wang and Marco Ballabio and Mao Wang and Lin, {Hung Hsuan} and Biswal, {Bishnu P.} and Xiaocang Han and Silvia Paasch and Eike Brunner and Pan Liu and Mingwei Chen and Mischa Bonn and Thomas Heine and Shengqiang Zhou and Enrique C{\'a}novas and Renhao Dong and Xinliang Feng",

note = "Funding Information: We thank financial support from EU Graphene Flagship, ERC Consolidator Grant (T2DCP), ERC Starting Grant (FC2DMOF, No. 852909), Coordination Networks: Building Blocks for Functional Systems (SPP 1928, COORNET) as well as the German Science Council, Center of Advancing Electronics Dresden, EXC1056, (cfaed), and OR 349/1. We acknowledge the Dresden Center for Nanoanalysis (DCN) at TUD; Dr. Philipp Schlender, Dr. Konrad Schneider (Leibniz Institute for Polymer Research, IPF, Dresden), Dr. Tilo L{\"u}bken, and Mr. Friedrich Schwotzer for the use of facilities. We also appreciate Mr. Ji Ma, Dr. Haixia Zhong, and Ms. Yu Zhang (UvA) for the MS, SEM, and XPS analysis, respectively. We thank Mr. Chi Xu (HZDR), Dr. Chongqing Yang, and Dr. Zhongquan Liao (IKTS) for the helpful discussions. Prof. T. Heine and Hung-Hsuan Lin acknowledge the Centre for Information Services and High-Performance Computing (ZIH) in Dresden, Germany, for the provided computational resources. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = oct,

day = "23",

doi = "10.1021/jacs.9b07644",

language = "English",

volume = "141",

pages = "16810--16816",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "42",

}

Wang, M, Ballabio, M, Wang, M, Lin, HH, Biswal, BP, Han, X, Paasch, S, Brunner, E, Liu, P, Chen, M, Bonn, M, Heine, T, Zhou, S, Cánovas, E, Dong, R & Feng, X 2019, 'Unveiling Electronic Properties in Metal-Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks', Journal of the American Chemical Society, vol. 141, no. 42, pp. 16810-16816. https://doi.org/10.1021/jacs.9b07644

TY - JOUR

T1 - Unveiling Electronic Properties in Metal-Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks

AU - Wang, Mingchao

AU - Ballabio, Marco

AU - Wang, Mao

AU - Lin, Hung Hsuan

AU - Biswal, Bishnu P.

AU - Han, Xiaocang

AU - Paasch, Silvia

AU - Brunner, Eike

AU - Liu, Pan

AU - Chen, Mingwei

AU - Bonn, Mischa

AU - Heine, Thomas

AU - Zhou, Shengqiang

AU - Cánovas, Enrique

AU - Dong, Renhao

AU - Feng, Xinliang

N1 - Funding Information: We thank financial support from EU Graphene Flagship, ERC Consolidator Grant (T2DCP), ERC Starting Grant (FC2DMOF, No. 852909), Coordination Networks: Building Blocks for Functional Systems (SPP 1928, COORNET) as well as the German Science Council, Center of Advancing Electronics Dresden, EXC1056, (cfaed), and OR 349/1. We acknowledge the Dresden Center for Nanoanalysis (DCN) at TUD; Dr. Philipp Schlender, Dr. Konrad Schneider (Leibniz Institute for Polymer Research, IPF, Dresden), Dr. Tilo Lübken, and Mr. Friedrich Schwotzer for the use of facilities. We also appreciate Mr. Ji Ma, Dr. Haixia Zhong, and Ms. Yu Zhang (UvA) for the MS, SEM, and XPS analysis, respectively. We thank Mr. Chi Xu (HZDR), Dr. Chongqing Yang, and Dr. Zhongquan Liao (IKTS) for the helpful discussions. Prof. T. Heine and Hung-Hsuan Lin acknowledge the Centre for Information Services and High-Performance Computing (ZIH) in Dresden, Germany, for the provided computational resources. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/10/23

Y1 - 2019/10/23

N2 - π-Conjugated two-dimensional covalent organic frameworks (2D COFs) are emerging as a novel class of electroactive materials for (opto)electronic and chemiresistive sensing applications. However, understanding the intricate interplay between chemistry, structure, and conductivity in π-conjugated 2D COFs remains elusive. Here, we report a detailed characterization for the electronic properties of two novel samples consisting of Zn- and Cu-phthalocyanine-based pyrazine-linked 2D COFs. These 2D COFs are synthesized by condensation of metal-phthalocyanine (M = Zn and Cu) and pyrene derivatives. The obtained polycrystalline-layered COFs are p-type semiconductors both with a band gap of ∼1.2 eV. A record device-relevant mobility up to ∼5 cm2/(V s) is resolved in the dc limit, which represents a lower threshold induced by charge carrier localization at crystalline grain boundaries. Hall effect measurements (dc limit) and terahertz (THz) spectroscopy (ac limit) in combination with density functional theory (DFT) calculations demonstrate that varying metal center from Cu to Zn in the phthalocyanine moiety has a negligible effect in the conductivity (∼5 × 10-7 S/cm), charge carrier density (∼1012 cm-3), charge carrier scattering rate (∼3 × 1013 s-1), and effective mass (∼2.3m0) of majority carriers (holes). Notably, charge carrier transport is found to be anisotropic, with hole mobilities being practically null in-plane and finite out-of-plane for these 2D COFs.

AB - π-Conjugated two-dimensional covalent organic frameworks (2D COFs) are emerging as a novel class of electroactive materials for (opto)electronic and chemiresistive sensing applications. However, understanding the intricate interplay between chemistry, structure, and conductivity in π-conjugated 2D COFs remains elusive. Here, we report a detailed characterization for the electronic properties of two novel samples consisting of Zn- and Cu-phthalocyanine-based pyrazine-linked 2D COFs. These 2D COFs are synthesized by condensation of metal-phthalocyanine (M = Zn and Cu) and pyrene derivatives. The obtained polycrystalline-layered COFs are p-type semiconductors both with a band gap of ∼1.2 eV. A record device-relevant mobility up to ∼5 cm2/(V s) is resolved in the dc limit, which represents a lower threshold induced by charge carrier localization at crystalline grain boundaries. Hall effect measurements (dc limit) and terahertz (THz) spectroscopy (ac limit) in combination with density functional theory (DFT) calculations demonstrate that varying metal center from Cu to Zn in the phthalocyanine moiety has a negligible effect in the conductivity (∼5 × 10-7 S/cm), charge carrier density (∼1012 cm-3), charge carrier scattering rate (∼3 × 1013 s-1), and effective mass (∼2.3m0) of majority carriers (holes). Notably, charge carrier transport is found to be anisotropic, with hole mobilities being practically null in-plane and finite out-of-plane for these 2D COFs.

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JO - Journal of the American Chemical Society

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IS - 42

ER -

Unveiling Electronic Properties in Metal-Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks

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