Effect of the thiol-thiolate equilibrium on the photophysical properties of aqueous CdSe/ZnS nanocrystal quantum dots

Sohee Jeong, Marc Achermann, Jagjit Nanda, Sergei Ivanov, Victor I Klimov, Jennifer A. Hollingsworth

Research output: Contribution to journalArticle

187 Citations (Scopus)

Abstract

We study the effect of thiols on the emission efficiency of aqueous CdSe/ZnS core/shell nanocrystal quantum dots (NQDs). We observe that the impact of thiol addition on emission quantum yields (QYs) is time-, concentration-, and pH-dependent. Further, we use a combination of time-resolved spectroscopic methods to determine the mechanism by which thiol addition can cause either increases or decreases in QYs. Specifically, through transient absorption measurements, we show that thiol addition can improve passivation of electron traps, increasing QYs at low thiol concentrations. Further, using nanosecond photoluminescence (PL), we observe that at higher thiol concentrations, hole traps are introduced that reduce PL QYs. Last, through a combination of pH-dependence and control studies (e.g., addition of 2-methyl thioethanol to an aqueous NQD solution and addition of dodecanethiol to a hexane NQD solution), we demonstrate that it is the ability of thiols in aqueous solution to generate thiolate that is the source of both favorable and adverse QY changes. Our results contribute to the understanding of the role of surface ligands, which is critical to the design of stable, high-quantum-yield, nonblinking NQDs.

Original languageEnglish
Pages (from-to)10126-10127
Number of pages2
JournalJournal of the American Chemical Society
Volume127
Issue number29
DOIs
Publication statusPublished - Jul 27 2005

Fingerprint

Quantum Dots
Quantum yield
Sulfhydryl Compounds
Nanoparticles
Nanocrystals
Semiconductor quantum dots
Photoluminescence
Hole traps
Electron traps
Hexane
Passivation
Hexanes
Ligands
Electrons

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Effect of the thiol-thiolate equilibrium on the photophysical properties of aqueous CdSe/ZnS nanocrystal quantum dots. / Jeong, Sohee; Achermann, Marc; Nanda, Jagjit; Ivanov, Sergei; Klimov, Victor I; Hollingsworth, Jennifer A.

In: Journal of the American Chemical Society, Vol. 127, No. 29, 27.07.2005, p. 10126-10127.

Research output: Contribution to journalArticle

Jeong, Sohee ; Achermann, Marc ; Nanda, Jagjit ; Ivanov, Sergei ; Klimov, Victor I ; Hollingsworth, Jennifer A. / Effect of the thiol-thiolate equilibrium on the photophysical properties of aqueous CdSe/ZnS nanocrystal quantum dots. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 29. pp. 10126-10127.
@article{a3467824e1d648319ec2326f51e75d1a,
title = "Effect of the thiol-thiolate equilibrium on the photophysical properties of aqueous CdSe/ZnS nanocrystal quantum dots",
abstract = "We study the effect of thiols on the emission efficiency of aqueous CdSe/ZnS core/shell nanocrystal quantum dots (NQDs). We observe that the impact of thiol addition on emission quantum yields (QYs) is time-, concentration-, and pH-dependent. Further, we use a combination of time-resolved spectroscopic methods to determine the mechanism by which thiol addition can cause either increases or decreases in QYs. Specifically, through transient absorption measurements, we show that thiol addition can improve passivation of electron traps, increasing QYs at low thiol concentrations. Further, using nanosecond photoluminescence (PL), we observe that at higher thiol concentrations, hole traps are introduced that reduce PL QYs. Last, through a combination of pH-dependence and control studies (e.g., addition of 2-methyl thioethanol to an aqueous NQD solution and addition of dodecanethiol to a hexane NQD solution), we demonstrate that it is the ability of thiols in aqueous solution to generate thiolate that is the source of both favorable and adverse QY changes. Our results contribute to the understanding of the role of surface ligands, which is critical to the design of stable, high-quantum-yield, nonblinking NQDs.",
author = "Sohee Jeong and Marc Achermann and Jagjit Nanda and Sergei Ivanov and Klimov, {Victor I} and Hollingsworth, {Jennifer A.}",
year = "2005",
month = "7",
day = "27",
doi = "10.1021/ja042591p",
language = "English",
volume = "127",
pages = "10126--10127",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "29",

}

TY - JOUR

T1 - Effect of the thiol-thiolate equilibrium on the photophysical properties of aqueous CdSe/ZnS nanocrystal quantum dots

AU - Jeong, Sohee

AU - Achermann, Marc

AU - Nanda, Jagjit

AU - Ivanov, Sergei

AU - Klimov, Victor I

AU - Hollingsworth, Jennifer A.

PY - 2005/7/27

Y1 - 2005/7/27

N2 - We study the effect of thiols on the emission efficiency of aqueous CdSe/ZnS core/shell nanocrystal quantum dots (NQDs). We observe that the impact of thiol addition on emission quantum yields (QYs) is time-, concentration-, and pH-dependent. Further, we use a combination of time-resolved spectroscopic methods to determine the mechanism by which thiol addition can cause either increases or decreases in QYs. Specifically, through transient absorption measurements, we show that thiol addition can improve passivation of electron traps, increasing QYs at low thiol concentrations. Further, using nanosecond photoluminescence (PL), we observe that at higher thiol concentrations, hole traps are introduced that reduce PL QYs. Last, through a combination of pH-dependence and control studies (e.g., addition of 2-methyl thioethanol to an aqueous NQD solution and addition of dodecanethiol to a hexane NQD solution), we demonstrate that it is the ability of thiols in aqueous solution to generate thiolate that is the source of both favorable and adverse QY changes. Our results contribute to the understanding of the role of surface ligands, which is critical to the design of stable, high-quantum-yield, nonblinking NQDs.

AB - We study the effect of thiols on the emission efficiency of aqueous CdSe/ZnS core/shell nanocrystal quantum dots (NQDs). We observe that the impact of thiol addition on emission quantum yields (QYs) is time-, concentration-, and pH-dependent. Further, we use a combination of time-resolved spectroscopic methods to determine the mechanism by which thiol addition can cause either increases or decreases in QYs. Specifically, through transient absorption measurements, we show that thiol addition can improve passivation of electron traps, increasing QYs at low thiol concentrations. Further, using nanosecond photoluminescence (PL), we observe that at higher thiol concentrations, hole traps are introduced that reduce PL QYs. Last, through a combination of pH-dependence and control studies (e.g., addition of 2-methyl thioethanol to an aqueous NQD solution and addition of dodecanethiol to a hexane NQD solution), we demonstrate that it is the ability of thiols in aqueous solution to generate thiolate that is the source of both favorable and adverse QY changes. Our results contribute to the understanding of the role of surface ligands, which is critical to the design of stable, high-quantum-yield, nonblinking NQDs.

UR - http://www.scopus.com/inward/record.url?scp=22944441670&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=22944441670&partnerID=8YFLogxK

U2 - 10.1021/ja042591p

DO - 10.1021/ja042591p

M3 - Article

VL - 127

SP - 10126

EP - 10127

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 29

ER -