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Title: Realizing nearly-free-electron like conduction band in a molecular film through mediating intermolecular van der Waals interactions

Abstract

Collective molecular physical properties can be enhanced from their intrinsic characteristics by templating at material interfaces. Here we report how a black phosphorous (BP) substrate concatenates a nearly-free-electron (NFE) like conduction band of a C 60 monolayer. Scanning tunneling microscopy reveals the C 60 lowest unoccupied molecular orbital (LUMO) band is strongly delocalized in two-dimensions, which is unprecedented for a molecular semiconductor. Experiment and theory show van der Waals forces between C 60 and BP reduce the inter-C 60 distance and cause mutual orientation, thereby optimizing the π-π wave function overlap and forming the NFE-like band. Electronic structure and carrier mobility calculations predict that the NFE band of C 60 acquires an effective mass of 0.53–0.70 m e ( m e is the mass of free electrons), and has carrier mobility of ~200 to 440 cm 2V -1s -1. The substrate-mediated intermolecular van der Waals interactions provide a route to enhance charge delocalization in fullerenes and other organic semiconductors.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [5]
  1. Wuhan Univ. (China). School of Physics and Technology and Key Lab. of Artificial Micro- and Nano-Structures of Ministry of Education
  2. Renmin Univ. of China, Beijing (China). Beijing Key Lab. of Optoelectronic Functional Materials & Micro-Nano Devices
  3. Mitsubishi Electric Research Lab., Cambridge, MA (United States)
  4. Univ. of Pittsburgh, PA (United States). Pittsburgh Quantum Inst.
  5. Wuhan Univ. (China). School of Physics and Technology and Key Lab. of Artificial Micro- and Nano-Structures of Ministry of Education, Inst. for Advanced Studies
Publication Date:
Research Org.:
Univ. of Pittsburgh, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; Chinese Academy of Sciences (CAS); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1610690
Grant/Contract Number:  
SC0002313; 2017YFA0303500; 2017YFA0303504; XDB30000000; 11574364; 11622437; 61674171; 16XNLQ01
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Science & Technology - Other Topics

Citation Formats

Cui, Xingxia, Han, Ding, Guo, Hongli, Zhou, Linwei, Qiao, Jingsi, Liu, Qing, Cui, Zhihao, Li, Yafei, Lin, Chungwei, Cao, Limin, Ji, Wei, Petek, Hrvoje, and Feng, Min. Realizing nearly-free-electron like conduction band in a molecular film through mediating intermolecular van der Waals interactions. United States: N. p., 2019. Web. doi:10.1038/s41467-019-11300-y.
Cui, Xingxia, Han, Ding, Guo, Hongli, Zhou, Linwei, Qiao, Jingsi, Liu, Qing, Cui, Zhihao, Li, Yafei, Lin, Chungwei, Cao, Limin, Ji, Wei, Petek, Hrvoje, & Feng, Min. Realizing nearly-free-electron like conduction band in a molecular film through mediating intermolecular van der Waals interactions. United States. doi:10.1038/s41467-019-11300-y.
Cui, Xingxia, Han, Ding, Guo, Hongli, Zhou, Linwei, Qiao, Jingsi, Liu, Qing, Cui, Zhihao, Li, Yafei, Lin, Chungwei, Cao, Limin, Ji, Wei, Petek, Hrvoje, and Feng, Min. Mon . "Realizing nearly-free-electron like conduction band in a molecular film through mediating intermolecular van der Waals interactions". United States. doi:10.1038/s41467-019-11300-y. https://www.osti.gov/servlets/purl/1610690.
@article{osti_1610690,
title = {Realizing nearly-free-electron like conduction band in a molecular film through mediating intermolecular van der Waals interactions},
author = {Cui, Xingxia and Han, Ding and Guo, Hongli and Zhou, Linwei and Qiao, Jingsi and Liu, Qing and Cui, Zhihao and Li, Yafei and Lin, Chungwei and Cao, Limin and Ji, Wei and Petek, Hrvoje and Feng, Min},
abstractNote = {Collective molecular physical properties can be enhanced from their intrinsic characteristics by templating at material interfaces. Here we report how a black phosphorous (BP) substrate concatenates a nearly-free-electron (NFE) like conduction band of a C60 monolayer. Scanning tunneling microscopy reveals the C60 lowest unoccupied molecular orbital (LUMO) band is strongly delocalized in two-dimensions, which is unprecedented for a molecular semiconductor. Experiment and theory show van der Waals forces between C60 and BP reduce the inter-C60 distance and cause mutual orientation, thereby optimizing the π-π wave function overlap and forming the NFE-like band. Electronic structure and carrier mobility calculations predict that the NFE band of C60 acquires an effective mass of 0.53–0.70 me (me is the mass of free electrons), and has carrier mobility of ~200 to 440 cm2V-1s-1. The substrate-mediated intermolecular van der Waals interactions provide a route to enhance charge delocalization in fullerenes and other organic semiconductors.},
doi = {10.1038/s41467-019-11300-y},
journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {7}
}

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