Dithienocarbazole-based ladder-type heptacyclic arenes with silicon, carbon, and nitrogen bridges

Synthesis, molecular properties, field-effect transistors, and photovoltaic applications

Jhong Sian Wu, Yen Ju Cheng, Tai Yen Lin, Chih Yu Chang, Peng I. Shih, Chain Shu Hsu

Research output: Contribution to journalArticle

79 Citations (Scopus)

Abstract

A new class of ladder-type dithienosilolo-carbazole (DTSC), dithienopyrrolo-carbazole (DTPC), and dithienocyclopenta-carbazole (DTCC) units is developed in which two outer thiophene subunits are covalently fastened to the central 2,7-carbazole cores by silicon, nitrogen, and carbon bridges, respectively. The heptacyclic multifused monomers are polymerized with the benzothiadiazole (BT) acceptor by palladium-catalyzed cross-coupling to afford three alternating donor-acceptor copolymers poly(dithienosilolo-carbazole-alt- benzothiadiazole) (PDTSCBT), poly(dithienocyclopenta-carbazole-alt- benzothiadiazole) (PDTCCBT), and poly(dithienopyrrolo-carbazole-alt- benzothiadiazole) (PDTPCBT). The silole units in DTSC possess electron-accepting ability that lowers the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of PDTSCBT, whereas stronger electron-donating ability of the pyrrole moiety in DTPC increases the HOMO and LUMO energy levels of PDTPCBT. The optical bandgaps (E g opt) deduced from the absorption edges of thin film spectra are in the following order: PDTSCBT (1.83 eV) > PDTCCBT (1.64 eV) > PDTPCBT (1.50 eV). This result indicated that the donor strength of the heptacyclic arenes is in the order: DTPC > DTCC > DTSC. The devices based on PDTSCBT and PDTCCBT exhibited high hole mobilities of 0.073 and 0.110 cm 2 V -1 s -1, respectively, which are among the highest performance from the OFET devices based on the amorphous donor-acceptor copolymers. The bulk heterojunction photovoltaic device using PDTSCBT as the p-type material delivered a promising efficiency of 5.2% with an enhanced open circuit voltage, V oc, of 0.82 V.

Original languageEnglish
Pages (from-to)1711-1722
Number of pages12
JournalAdvanced Functional Materials
Volume22
Issue number8
DOIs
Publication statusPublished - Apr 24 2012
Externally publishedYes

Fingerprint

carbazoles
molecular properties
Ladders
Molecular orbitals
Silicon
Field effect transistors
ladders
Nitrogen
Carbon
field effect transistors
nitrogen
carbon
silicon
synthesis
Electron energy levels
Copolymers
Organic field effect transistors
Hole mobility
Electrons
Optical band gaps

Keywords

  • field-effect transistors
  • ladder-type structures
  • polymer solar cells

ASJC Scopus subject areas

  • Biomaterials
  • Electrochemistry
  • Condensed Matter Physics
  • Electronic, Optical and Magnetic Materials

Cite this

Dithienocarbazole-based ladder-type heptacyclic arenes with silicon, carbon, and nitrogen bridges : Synthesis, molecular properties, field-effect transistors, and photovoltaic applications. / Wu, Jhong Sian; Cheng, Yen Ju; Lin, Tai Yen; Chang, Chih Yu; Shih, Peng I.; Hsu, Chain Shu.

In: Advanced Functional Materials, Vol. 22, No. 8, 24.04.2012, p. 1711-1722.

Research output: Contribution to journalArticle

@article{c5fc4dbdb3fb4990b7c408ae968faf40,
title = "Dithienocarbazole-based ladder-type heptacyclic arenes with silicon, carbon, and nitrogen bridges: Synthesis, molecular properties, field-effect transistors, and photovoltaic applications",
abstract = "A new class of ladder-type dithienosilolo-carbazole (DTSC), dithienopyrrolo-carbazole (DTPC), and dithienocyclopenta-carbazole (DTCC) units is developed in which two outer thiophene subunits are covalently fastened to the central 2,7-carbazole cores by silicon, nitrogen, and carbon bridges, respectively. The heptacyclic multifused monomers are polymerized with the benzothiadiazole (BT) acceptor by palladium-catalyzed cross-coupling to afford three alternating donor-acceptor copolymers poly(dithienosilolo-carbazole-alt- benzothiadiazole) (PDTSCBT), poly(dithienocyclopenta-carbazole-alt- benzothiadiazole) (PDTCCBT), and poly(dithienopyrrolo-carbazole-alt- benzothiadiazole) (PDTPCBT). The silole units in DTSC possess electron-accepting ability that lowers the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of PDTSCBT, whereas stronger electron-donating ability of the pyrrole moiety in DTPC increases the HOMO and LUMO energy levels of PDTPCBT. The optical bandgaps (E g opt) deduced from the absorption edges of thin film spectra are in the following order: PDTSCBT (1.83 eV) > PDTCCBT (1.64 eV) > PDTPCBT (1.50 eV). This result indicated that the donor strength of the heptacyclic arenes is in the order: DTPC > DTCC > DTSC. The devices based on PDTSCBT and PDTCCBT exhibited high hole mobilities of 0.073 and 0.110 cm 2 V -1 s -1, respectively, which are among the highest performance from the OFET devices based on the amorphous donor-acceptor copolymers. The bulk heterojunction photovoltaic device using PDTSCBT as the p-type material delivered a promising efficiency of 5.2{\%} with an enhanced open circuit voltage, V oc, of 0.82 V.",
keywords = "field-effect transistors, ladder-type structures, polymer solar cells",
author = "Wu, {Jhong Sian} and Cheng, {Yen Ju} and Lin, {Tai Yen} and Chang, {Chih Yu} and Shih, {Peng I.} and Hsu, {Chain Shu}",
year = "2012",
month = "4",
day = "24",
doi = "10.1002/adfm.201102906",
language = "English",
volume = "22",
pages = "1711--1722",
journal = "Advanced Materials for Optics and Electronics",
issn = "1057-9257",
publisher = "Wiley-Blackwell",
number = "8",

}

TY - JOUR

T1 - Dithienocarbazole-based ladder-type heptacyclic arenes with silicon, carbon, and nitrogen bridges

T2 - Synthesis, molecular properties, field-effect transistors, and photovoltaic applications

AU - Wu, Jhong Sian

AU - Cheng, Yen Ju

AU - Lin, Tai Yen

AU - Chang, Chih Yu

AU - Shih, Peng I.

AU - Hsu, Chain Shu

PY - 2012/4/24

Y1 - 2012/4/24

N2 - A new class of ladder-type dithienosilolo-carbazole (DTSC), dithienopyrrolo-carbazole (DTPC), and dithienocyclopenta-carbazole (DTCC) units is developed in which two outer thiophene subunits are covalently fastened to the central 2,7-carbazole cores by silicon, nitrogen, and carbon bridges, respectively. The heptacyclic multifused monomers are polymerized with the benzothiadiazole (BT) acceptor by palladium-catalyzed cross-coupling to afford three alternating donor-acceptor copolymers poly(dithienosilolo-carbazole-alt- benzothiadiazole) (PDTSCBT), poly(dithienocyclopenta-carbazole-alt- benzothiadiazole) (PDTCCBT), and poly(dithienopyrrolo-carbazole-alt- benzothiadiazole) (PDTPCBT). The silole units in DTSC possess electron-accepting ability that lowers the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of PDTSCBT, whereas stronger electron-donating ability of the pyrrole moiety in DTPC increases the HOMO and LUMO energy levels of PDTPCBT. The optical bandgaps (E g opt) deduced from the absorption edges of thin film spectra are in the following order: PDTSCBT (1.83 eV) > PDTCCBT (1.64 eV) > PDTPCBT (1.50 eV). This result indicated that the donor strength of the heptacyclic arenes is in the order: DTPC > DTCC > DTSC. The devices based on PDTSCBT and PDTCCBT exhibited high hole mobilities of 0.073 and 0.110 cm 2 V -1 s -1, respectively, which are among the highest performance from the OFET devices based on the amorphous donor-acceptor copolymers. The bulk heterojunction photovoltaic device using PDTSCBT as the p-type material delivered a promising efficiency of 5.2% with an enhanced open circuit voltage, V oc, of 0.82 V.

AB - A new class of ladder-type dithienosilolo-carbazole (DTSC), dithienopyrrolo-carbazole (DTPC), and dithienocyclopenta-carbazole (DTCC) units is developed in which two outer thiophene subunits are covalently fastened to the central 2,7-carbazole cores by silicon, nitrogen, and carbon bridges, respectively. The heptacyclic multifused monomers are polymerized with the benzothiadiazole (BT) acceptor by palladium-catalyzed cross-coupling to afford three alternating donor-acceptor copolymers poly(dithienosilolo-carbazole-alt- benzothiadiazole) (PDTSCBT), poly(dithienocyclopenta-carbazole-alt- benzothiadiazole) (PDTCCBT), and poly(dithienopyrrolo-carbazole-alt- benzothiadiazole) (PDTPCBT). The silole units in DTSC possess electron-accepting ability that lowers the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of PDTSCBT, whereas stronger electron-donating ability of the pyrrole moiety in DTPC increases the HOMO and LUMO energy levels of PDTPCBT. The optical bandgaps (E g opt) deduced from the absorption edges of thin film spectra are in the following order: PDTSCBT (1.83 eV) > PDTCCBT (1.64 eV) > PDTPCBT (1.50 eV). This result indicated that the donor strength of the heptacyclic arenes is in the order: DTPC > DTCC > DTSC. The devices based on PDTSCBT and PDTCCBT exhibited high hole mobilities of 0.073 and 0.110 cm 2 V -1 s -1, respectively, which are among the highest performance from the OFET devices based on the amorphous donor-acceptor copolymers. The bulk heterojunction photovoltaic device using PDTSCBT as the p-type material delivered a promising efficiency of 5.2% with an enhanced open circuit voltage, V oc, of 0.82 V.

KW - field-effect transistors

KW - ladder-type structures

KW - polymer solar cells

UR - http://www.scopus.com/inward/record.url?scp=84859845866&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84859845866&partnerID=8YFLogxK

U2 - 10.1002/adfm.201102906

DO - 10.1002/adfm.201102906

M3 - Article

VL - 22

SP - 1711

EP - 1722

JO - Advanced Materials for Optics and Electronics

JF - Advanced Materials for Optics and Electronics

SN - 1057-9257

IS - 8

ER -