Parameters affecting electron injection dynamics from ruthenium dyes to titanium dioxide nanocrystalline thin film

John B. Asbury, Neil A. Anderson, Encai Hao, Xin Ai, Tianquan Lian

Research output: Contribution to journalArticle

197 Citations (Scopus)

Abstract

Electron injection rates from Ru(dcbpy)2(X)2 [X = 2NCS, 2CN, and dcbpy; dcbpy = 2,2′-bipyridine-4,4′-carboxylate] (called Ru535 or Ru N3, Ru505, and Ru470) to TiO2 nanocrystalline thin films are examined as a function of adsorbate redox potential, pH of the solution, excitation wavelength, and solvent. For all three dyes, the injection kinetics are biphasic, consisting of a distinct ultrafast component (<100 fs) and slower components. Under different experimental conditions, the partitioning between these two components and the rate of the slow components change, but the rate of the fast component shows no noticeable variations within the ∼200 fs time resolution of the measurement. When Ru535, Ru505, and Ru470 were compared at the same pH, increasing amplitude and decreasing rate of slow component were observed, correlating with less negative excited-state redox potentials in these dyes. An analogous trend was seen for RuN3/TiO2 by increasing the pH of the solution from pH = 2 to 8 and changing from pH = 2 aqueous solution to a (1:1) ethylene/propylene carbonate mixture. The injection dynamics are also dependent on excitation wavelength. The relative amplitude of the slow component increases when the excitation wavelength is changed from 400 to 630 nm. All data can be described by a two-state injection model, which attributes the fast (<100 fs) component to injection from a nonthermalized excited state and the slow component to injection from the thermalized excited state. The partitioning between these two components and the rate of the slow components depend on the relative energetics between dye excited states and the conduction band edge.

Original languageEnglish (US)
Pages (from-to)7376-7386
Number of pages11
JournalJournal of Physical Chemistry B
Volume107
Issue number30
StatePublished - Jul 31 2003

Fingerprint

Electron injection
Ruthenium
Excited states
titanium oxides
Titanium dioxide
ruthenium
Coloring Agents
Dyes
dyes
injection
Thin films
thin films
Wavelength
electrons
excitation
Adsorbates
Conduction bands
Propylene
Carbonates
Ethylene

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Asbury, John B. ; Anderson, Neil A. ; Hao, Encai ; Ai, Xin ; Lian, Tianquan. / Parameters affecting electron injection dynamics from ruthenium dyes to titanium dioxide nanocrystalline thin film. In: Journal of Physical Chemistry B. 2003 ; Vol. 107, No. 30. pp. 7376-7386.
@article{0b321463fed04266976aaf2feb0176ac,
title = "Parameters affecting electron injection dynamics from ruthenium dyes to titanium dioxide nanocrystalline thin film",
abstract = "Electron injection rates from Ru(dcbpy)2(X)2 [X = 2NCS, 2CN, and dcbpy; dcbpy = 2,2′-bipyridine-4,4′-carboxylate] (called Ru535 or Ru N3, Ru505, and Ru470) to TiO2 nanocrystalline thin films are examined as a function of adsorbate redox potential, pH of the solution, excitation wavelength, and solvent. For all three dyes, the injection kinetics are biphasic, consisting of a distinct ultrafast component (<100 fs) and slower components. Under different experimental conditions, the partitioning between these two components and the rate of the slow components change, but the rate of the fast component shows no noticeable variations within the ∼200 fs time resolution of the measurement. When Ru535, Ru505, and Ru470 were compared at the same pH, increasing amplitude and decreasing rate of slow component were observed, correlating with less negative excited-state redox potentials in these dyes. An analogous trend was seen for RuN3/TiO2 by increasing the pH of the solution from pH = 2 to 8 and changing from pH = 2 aqueous solution to a (1:1) ethylene/propylene carbonate mixture. The injection dynamics are also dependent on excitation wavelength. The relative amplitude of the slow component increases when the excitation wavelength is changed from 400 to 630 nm. All data can be described by a two-state injection model, which attributes the fast (<100 fs) component to injection from a nonthermalized excited state and the slow component to injection from the thermalized excited state. The partitioning between these two components and the rate of the slow components depend on the relative energetics between dye excited states and the conduction band edge.",
author = "Asbury, {John B.} and Anderson, {Neil A.} and Encai Hao and Xin Ai and Tianquan Lian",
year = "2003",
month = "7",
day = "31",
language = "English (US)",
volume = "107",
pages = "7376--7386",
journal = "Journal of Physical Chemistry B",
issn = "1520-6106",
number = "30",

}

Parameters affecting electron injection dynamics from ruthenium dyes to titanium dioxide nanocrystalline thin film. / Asbury, John B.; Anderson, Neil A.; Hao, Encai; Ai, Xin; Lian, Tianquan.

In: Journal of Physical Chemistry B, Vol. 107, No. 30, 31.07.2003, p. 7376-7386.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Parameters affecting electron injection dynamics from ruthenium dyes to titanium dioxide nanocrystalline thin film

AU - Asbury, John B.

AU - Anderson, Neil A.

AU - Hao, Encai

AU - Ai, Xin

AU - Lian, Tianquan

PY - 2003/7/31

Y1 - 2003/7/31

N2 - Electron injection rates from Ru(dcbpy)2(X)2 [X = 2NCS, 2CN, and dcbpy; dcbpy = 2,2′-bipyridine-4,4′-carboxylate] (called Ru535 or Ru N3, Ru505, and Ru470) to TiO2 nanocrystalline thin films are examined as a function of adsorbate redox potential, pH of the solution, excitation wavelength, and solvent. For all three dyes, the injection kinetics are biphasic, consisting of a distinct ultrafast component (<100 fs) and slower components. Under different experimental conditions, the partitioning between these two components and the rate of the slow components change, but the rate of the fast component shows no noticeable variations within the ∼200 fs time resolution of the measurement. When Ru535, Ru505, and Ru470 were compared at the same pH, increasing amplitude and decreasing rate of slow component were observed, correlating with less negative excited-state redox potentials in these dyes. An analogous trend was seen for RuN3/TiO2 by increasing the pH of the solution from pH = 2 to 8 and changing from pH = 2 aqueous solution to a (1:1) ethylene/propylene carbonate mixture. The injection dynamics are also dependent on excitation wavelength. The relative amplitude of the slow component increases when the excitation wavelength is changed from 400 to 630 nm. All data can be described by a two-state injection model, which attributes the fast (<100 fs) component to injection from a nonthermalized excited state and the slow component to injection from the thermalized excited state. The partitioning between these two components and the rate of the slow components depend on the relative energetics between dye excited states and the conduction band edge.

AB - Electron injection rates from Ru(dcbpy)2(X)2 [X = 2NCS, 2CN, and dcbpy; dcbpy = 2,2′-bipyridine-4,4′-carboxylate] (called Ru535 or Ru N3, Ru505, and Ru470) to TiO2 nanocrystalline thin films are examined as a function of adsorbate redox potential, pH of the solution, excitation wavelength, and solvent. For all three dyes, the injection kinetics are biphasic, consisting of a distinct ultrafast component (<100 fs) and slower components. Under different experimental conditions, the partitioning between these two components and the rate of the slow components change, but the rate of the fast component shows no noticeable variations within the ∼200 fs time resolution of the measurement. When Ru535, Ru505, and Ru470 were compared at the same pH, increasing amplitude and decreasing rate of slow component were observed, correlating with less negative excited-state redox potentials in these dyes. An analogous trend was seen for RuN3/TiO2 by increasing the pH of the solution from pH = 2 to 8 and changing from pH = 2 aqueous solution to a (1:1) ethylene/propylene carbonate mixture. The injection dynamics are also dependent on excitation wavelength. The relative amplitude of the slow component increases when the excitation wavelength is changed from 400 to 630 nm. All data can be described by a two-state injection model, which attributes the fast (<100 fs) component to injection from a nonthermalized excited state and the slow component to injection from the thermalized excited state. The partitioning between these two components and the rate of the slow components depend on the relative energetics between dye excited states and the conduction band edge.

UR - http://www.scopus.com/inward/record.url?scp=0041696790&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0041696790&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0041696790

VL - 107

SP - 7376

EP - 7386

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 30

ER -