Site-specific chemical doping reveals electron atmospheres at the surfaces of organic semiconductor crystals

Tao He; Matthias Stolte; Yan Wang; Rebecca Renner; P. Paul Ruden; Frank Würthner; C. Daniel Frisbie

doi:10.1038/s41563-021-01079-z

Site-specific chemical doping reveals electron atmospheres at the surfaces of organic semiconductor crystals

Tao He, Matthias Stolte, Yan Wang, Rebecca Renner, P. Paul Ruden, Frank Würthner, C. Daniel Frisbie

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

33 Scopus citations

Abstract

Chemical doping controls the electronic properties of organic semiconductors, but so far, doping protocols and mechanisms are less developed than in conventional semiconductors. Here we describe a unique, site-specific, n-type surface doping mechanism for single crystals of two benchmark organic semiconductors that produces dramatic improvement in electron transport and provides unprecedented evidence for doping-induced space charge. The surface doping chemistry specifically targets crystallographic step edges, which are known electron traps, simultaneously passivating the traps and releasing itinerant electrons. The effect on electron transport is profound: field-effect electron mobility increases by as much as a factor of ten, and its temperature-dependent behaviour switches from thermally activated to band-like. Our findings suggest new site-specific strategies to dope organic semiconductors that differ from the conventional redox chemistry of randomly distributed substitutional impurities. Critically, they also verify the presence of doping-induced electron atmospheres, confirming long-standing expectations for organic systems from conventional solid-state theory.

Original language	English (US)
Pages (from-to)	1532-1538
Number of pages	7
Journal	Nature Materials
Volume	20
Issue number	11
DOIs	https://doi.org/10.1038/s41563-021-01079-z https://doi.org/10.1038/s41563-021-01079-z
State	Published - Nov 2021

Bibliographical note

Funding Information:
This work was supported primarily by the MRSEC programme of the National Science Foundation (NSF) under grant no. DMR-2011401 (T.H.). C.D.F. also acknowledges partial support from grant no. NSF DMR-1806419 and the University of Minnesota (P.P.R. and Y.W.). Parts of this work were carried out in the College of Science and Engineering Characterization Facility, University of Minnesota, which has received capital equipment funding from the NSF through the UMN MRSEC programme under award no. DMR-2011401, and in the Minnesota Nano Center, which is supported by NSF through the National Nano Coordinated Infrastructure Network, under award no. ECCS-2025124. Parts of this work were also carried out at the Center for Nanosystems Chemistry at the Universität Würzburg, which has received funds from the Bavarian State Ministry of Science and Arts in the framework of the research programme ‘Solar Technologies Go Hybrid’ (F.W.). Some of the SKPM measurements were performed at Shandong University, supported by the National Natural Science Foundation of China grant no. 62074093 (T.H.). T.H. also acknowledges support from the Qilu Young Scholars Programme of Shandong University.

Publisher Copyright:
© 2021, The Author(s), under exclusive licence to Springer Nature Limited.

MRSEC Support

Primary

PubMed: MeSH publication types

Journal Article

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Publisher link

https://www.nature.com/articles/s41563-021-01079-z

Find It

Find It at U of M Libraries

Cite this

@article{d2f0f627490f4c4d9b8b271792b834b3,

title = "Site-specific chemical doping reveals electron atmospheres at the surfaces of organic semiconductor crystals",

abstract = "Chemical doping controls the electronic properties of organic semiconductors, but so far, doping protocols and mechanisms are less developed than in conventional semiconductors. Here we describe a unique, site-specific, n-type surface doping mechanism for single crystals of two benchmark organic semiconductors that produces dramatic improvement in electron transport and provides unprecedented evidence for doping-induced space charge. The surface doping chemistry specifically targets crystallographic step edges, which are known electron traps, simultaneously passivating the traps and releasing itinerant electrons. The effect on electron transport is profound: field-effect electron mobility increases by as much as a factor of ten, and its temperature-dependent behaviour switches from thermally activated to band-like. Our findings suggest new site-specific strategies to dope organic semiconductors that differ from the conventional redox chemistry of randomly distributed substitutional impurities. Critically, they also verify the presence of doping-induced electron atmospheres, confirming long-standing expectations for organic systems from conventional solid-state theory.",

author = "Tao He and Matthias Stolte and Yan Wang and Rebecca Renner and Ruden, {P. Paul} and Frank W{\"u}rthner and Frisbie, {C. Daniel}",

note = "Funding Information: This work was supported primarily by the MRSEC programme of the National Science Foundation (NSF) under grant no. DMR-2011401 (T.H.). C.D.F. also acknowledges partial support from grant no. NSF DMR-1806419 and the University of Minnesota (P.P.R. and Y.W.). Parts of this work were carried out in the College of Science and Engineering Characterization Facility, University of Minnesota, which has received capital equipment funding from the NSF through the UMN MRSEC programme under award no. DMR-2011401, and in the Minnesota Nano Center, which is supported by NSF through the National Nano Coordinated Infrastructure Network, under award no. ECCS-2025124. Parts of this work were also carried out at the Center for Nanosystems Chemistry at the Universit{\"a}t W{\"u}rzburg, which has received funds from the Bavarian State Ministry of Science and Arts in the framework of the research programme {\textquoteleft}Solar Technologies Go Hybrid{\textquoteright} (F.W.). Some of the SKPM measurements were performed at Shandong University, supported by the National Natural Science Foundation of China grant no. 62074093 (T.H.). T.H. also acknowledges support from the Qilu Young Scholars Programme of Shandong University. Publisher Copyright: {\textcopyright} 2021, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2021",

month = nov,

doi = "10.1038/s41563-021-01079-z",

language = "English (US)",

volume = "20",

pages = "1532--1538",

journal = "Nature Materials",

issn = "1476-1122",

publisher = "Nature Publishing Group",

number = "11",

}

TY - JOUR

T1 - Site-specific chemical doping reveals electron atmospheres at the surfaces of organic semiconductor crystals

AU - He, Tao

AU - Stolte, Matthias

AU - Wang, Yan

AU - Renner, Rebecca

AU - Ruden, P. Paul

AU - Würthner, Frank

AU - Frisbie, C. Daniel

N1 - Funding Information: This work was supported primarily by the MRSEC programme of the National Science Foundation (NSF) under grant no. DMR-2011401 (T.H.). C.D.F. also acknowledges partial support from grant no. NSF DMR-1806419 and the University of Minnesota (P.P.R. and Y.W.). Parts of this work were carried out in the College of Science and Engineering Characterization Facility, University of Minnesota, which has received capital equipment funding from the NSF through the UMN MRSEC programme under award no. DMR-2011401, and in the Minnesota Nano Center, which is supported by NSF through the National Nano Coordinated Infrastructure Network, under award no. ECCS-2025124. Parts of this work were also carried out at the Center for Nanosystems Chemistry at the Universität Würzburg, which has received funds from the Bavarian State Ministry of Science and Arts in the framework of the research programme ‘Solar Technologies Go Hybrid’ (F.W.). Some of the SKPM measurements were performed at Shandong University, supported by the National Natural Science Foundation of China grant no. 62074093 (T.H.). T.H. also acknowledges support from the Qilu Young Scholars Programme of Shandong University. Publisher Copyright: © 2021, The Author(s), under exclusive licence to Springer Nature Limited.

PY - 2021/11

Y1 - 2021/11

N2 - Chemical doping controls the electronic properties of organic semiconductors, but so far, doping protocols and mechanisms are less developed than in conventional semiconductors. Here we describe a unique, site-specific, n-type surface doping mechanism for single crystals of two benchmark organic semiconductors that produces dramatic improvement in electron transport and provides unprecedented evidence for doping-induced space charge. The surface doping chemistry specifically targets crystallographic step edges, which are known electron traps, simultaneously passivating the traps and releasing itinerant electrons. The effect on electron transport is profound: field-effect electron mobility increases by as much as a factor of ten, and its temperature-dependent behaviour switches from thermally activated to band-like. Our findings suggest new site-specific strategies to dope organic semiconductors that differ from the conventional redox chemistry of randomly distributed substitutional impurities. Critically, they also verify the presence of doping-induced electron atmospheres, confirming long-standing expectations for organic systems from conventional solid-state theory.

AB - Chemical doping controls the electronic properties of organic semiconductors, but so far, doping protocols and mechanisms are less developed than in conventional semiconductors. Here we describe a unique, site-specific, n-type surface doping mechanism for single crystals of two benchmark organic semiconductors that produces dramatic improvement in electron transport and provides unprecedented evidence for doping-induced space charge. The surface doping chemistry specifically targets crystallographic step edges, which are known electron traps, simultaneously passivating the traps and releasing itinerant electrons. The effect on electron transport is profound: field-effect electron mobility increases by as much as a factor of ten, and its temperature-dependent behaviour switches from thermally activated to band-like. Our findings suggest new site-specific strategies to dope organic semiconductors that differ from the conventional redox chemistry of randomly distributed substitutional impurities. Critically, they also verify the presence of doping-induced electron atmospheres, confirming long-standing expectations for organic systems from conventional solid-state theory.

UR - http://www.scopus.com/inward/record.url?scp=85113912882&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85113912882&partnerID=8YFLogxK

U2 - 10.1038/s41563-021-01079-z

DO - 10.1038/s41563-021-01079-z

M3 - Article

C2 - 34462569

SN - 1476-1122

VL - 20

SP - 1532

EP - 1538

JO - Nature Materials

JF - Nature Materials

IS - 11

ER -

Site-specific chemical doping reveals electron atmospheres at the surfaces of organic semiconductor crystals

Abstract

Bibliographical note

MRSEC Support

PubMed: MeSH publication types

UN SDGs

Publisher link

Find It

Other files and links

Fingerprint

IRG-1: Ionic Control of Materials

University of Minnesota Materials Research Science and Engineering Center (DMR-2011401)

Source data for “Site-Specific Chemical Doping Reveals Electron Atmospheres at the Surfaces of Organic Semiconductor Crystals”

Cite this

Site-specific chemical doping reveals electron atmospheres at the surfaces of organic semiconductor crystals

Abstract

Bibliographical note

MRSEC Support

PubMed: MeSH publication types

UN SDGs

Publisher link

Find It

Other files and links

Fingerprint

Projects

IRG-1: Ionic Control of Materials

University of Minnesota Materials Research Science and Engineering Center (DMR-2011401)

Datasets

Source data for “Site-Specific Chemical Doping Reveals Electron Atmospheres at the Surfaces of Organic Semiconductor Crystals”

Cite this