Electroabsorption spectroscopy of luminescent and nonluminescent π-conjugated polymers

Liess, M.; Jeglinski, S.; Vardeny, Z. V.; Ozaki, M.; Yoshino, K.; Ding, Y.; Barton, T.

doi:https://doi.org/10.1103/PhysRevB.56.15712

Electroabsorption spectroscopy of luminescent and nonluminescent π-conjugated polymers

Liess, M.; Jeglinski, S.; Vardeny, Z. V. et al.

Physical Review B - Condensed Matter and Materials Physics, 1997, 56(24), 15712-15724

Number of Access:426（2025-09-02 10:20 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/75859

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Title	Electroabsorption spectroscopy of luminescent and nonluminescent π-conjugated polymers
Creator	CreatorName Liess, M.
	CreatorName Jeglinski, S.
	CreatorName Vardeny, Z. V.
	NRID 1000050204186 1000050204186 ORCID 0000-0002-9556-4225 0000-0002-9556-4225 researchmap permalink read0014092 read0014092 Scopus Author ID 55490143900 55490143900 CreatorName Ozaki, M.
	NRID 1000070029205 1000070029205 CreatorName Yoshino, K.
	CreatorName Ding, Y.
	CreatorName Barton, T.
Abstract	We have measured the quadratic electroabsorption (EA) spectrum of a variety of soluble luminescent and nonluminescent π-conjugated polymer films in the spectral range of 1.5–4.5 eV. The luminescent polymers include MEH and DOO derivatives of poly(phenylene-vinylene), poly(phenylene ethylene), and polythiophene; the nonluminescent polymers include poly(diethynyl silane) and monosubstituted polyacetylene. All EA spectra show a Stark shift of the low-lying odd-parity exciton (1Bu) and imply the presence of phonon sidebands. There are also higher-energy bands due to transfer of oscillator strength to even-parity exciton states (Ag), the strongest of which (mAg) is located at an energy about 1.3 times that of the 1Bu exciton in both luminescent and nonluminescent polymers; in the luminescent polymers the EA spectra also show a second prominent Ag state (kAg) at an energy of about 1.6 times that of the 1Bu . We have successfully fitted the EA spectra by calculating the imaginary part of the third order optical susceptibility, Im[x^3(-ω;ω,0,0)], using a summation over states model dominated by the ground state, the 1Bu exciton, two strongly coupled Ag states (mAg and kAg), and their most strongly coupled vibrations, using Frank-Condon overlap integrals. A distribution of conjugation lengths, which results in a distribution of excited state energies, was also incorporated into the model. The decomposition of the EA spectra due to the conjugation length distribution was then used to calculate the 1Bu exciton polarizability (Δp) using first derivative analysis. For the longest conjugation lengths in our films, we found Δp to be of order 10^4 (Å)^3 in luminescent polymers and 10^3 Å^3 in nonluminescent polymers, respectively, in good agreement with recent subnanosecond transient photoconductivity measurements. We also found that the Huang-Rhys parameter of the 1Bu exciton varies between 0.25 and 0.9, being in general smaller for the luminescent polymers. The consequent exciton relaxation energies were calculated to be of order 100 meV.
Publisher	American Physical Society
Source Title	Physical Review B - Condensed Matter and Materials Physics
Volume (Issue)	56(24)
Page	15712-15724
Date of Issued	1997-12-15
Language	English
Handle URL	https://hdl.handle.net/11094/75859
PISSN	24699950
eISSN	24699969
NCID	AA11187113
Relation.isIdenticalTo	DOI (Publisher Version) https://doi.org/10.1103/PhysRevB.56.15712
Access Rights	open access
CopyRight	Copyright (1997) by the American Physical Society
oaire:version	Version of Record
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCMI Type	Text
DCTERMS.bibliographicCitation	Physical Review B - Condensed Matter and Materials Physics. 1997, 56(24), p. 15712-15724
DC.title	Electroabsorption spectroscopy of luminescent and nonluminescent π-conjugated polymers
DC.creator	Liess, M.
	Jeglinski, S.
	Vardeny, Z. V.
	Ozaki, M.
	Yoshino, K.
	Ding, Y.
	Barton, T.
DC.publisher	American Physical Society
DC.language' scheme='DCTERMS.RFC1766	English
DC.type' scheme='DCTERMS.DCMIType	Text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	1997-12-15
DC.identifier	https://doi.org/10.1103/PhysRevB.56.15712
DCTERMS.abstract	We have measured the quadratic electroabsorption (EA) spectrum of a variety of soluble luminescent and nonluminescent π-conjugated polymer films in the spectral range of 1.5–4.5 eV. The luminescent polymers include MEH and DOO derivatives of poly(phenylene-vinylene), poly(phenylene ethylene), and polythiophene; the nonluminescent polymers include poly(diethynyl silane) and monosubstituted polyacetylene. All EA spectra show a Stark shift of the low-lying odd-parity exciton (1Bu) and imply the presence of phonon sidebands. There are also higher-energy bands due to transfer of oscillator strength to even-parity exciton states (Ag), the strongest of which (mAg) is located at an energy about 1.3 times that of the 1Bu exciton in both luminescent and nonluminescent polymers; in the luminescent polymers the EA spectra also show a second prominent Ag state (kAg) at an energy of about 1.6 times that of the 1Bu . We have successfully fitted the EA spectra by calculating the imaginary part of the third order optical susceptibility, Im[x^3(-ω;ω,0,0)], using a summation over states model dominated by the ground state, the 1Bu exciton, two strongly coupled Ag states (mAg and kAg), and their most strongly coupled vibrations, using Frank-Condon overlap integrals. A distribution of conjugation lengths, which results in a distribution of excited state energies, was also incorporated into the model. The decomposition of the EA spectra due to the conjugation length distribution was then used to calculate the 1Bu exciton polarizability (Δp) using first derivative analysis. For the longest conjugation lengths in our films, we found Δp to be of order 10^4 (Å)^3 in luminescent polymers and 10^3 Å^3 in nonluminescent polymers, respectively, in good agreement with recent subnanosecond transient photoconductivity measurements. We also found that the Huang-Rhys parameter of the 1Bu exciton varies between 0.25 and 0.9, being in general smaller for the luminescent polymers. The consequent exciton relaxation energies were calculated to be of order 100 meV.
DC.rights	Copyright (1997) by the American Physical Society
DC.format	75859
citation_title	Electroabsorption spectroscopy of luminescent and nonluminescent π-conjugated polymers
citation_author	Liess, M.
	Jeglinski, S.
	Vardeny, Z. V.
	Ozaki, M.
	Yoshino, K.
	Ding, Y.
	Barton, T.
citation_publisher	American Physical Society
citation_language	English
citation_date	1997-12-15
citation_journal_title	Physical Review B - Condensed Matter and Materials Physics
citation_volume	56
citation_issue	24
citation_firstpage	15712
citation_lastpage	15724
citation_doi	https://doi.org/10.1103/PhysRevB.56.15712
citation_public_url	https://hdl.handle.net/11094/75859

Electroabsorption spectroscopy of luminescent and nonluminescent π-conjugated polymers

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