Skip to main content
SpringerLink
Log in

Electron transfer dynamics of single quantum dots on the (110) surface of a rutile TiO2 single crystal

  • Communications
  • Published:
Science China Chemistry Aims and scope Submit manuscript

Abstract

The interfacial electron transfer (IET) dynamics of single CdSe core/multilayer shell (CdS2MLZnCdS1MLZnS1ML) quantum dots (QDs) on the (110) surface of a rutile TiO2 single crystal and TiO2 nanoparticles have been compared. The fluorescence decay rates of single QDs on TiO2 are faster than those on glass, an insulating substrate, due to IET from the QDs to TiO2. Whereas the average IET rates are similar for QDs on the single crystal and nanoparticles, the distribution of IET rates is much broader in the latter, indicating a broad distribution of QD adsorption sites on the TiO2 nanoparticles.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Huynh WU, Dittmer JJ, Alivisatos AP. Hybrid nanorod-polymer solar cells. Science, 2002, 295: 2425–2427

    Article  CAS  Google Scholar 

  2. Robel I, Subramanian V, Kuno M, Kamat PV. Quantum dot solar cells. Harvesting light energy with Cdse nanocrystals molecularly linked to mesoscopic TiO2 films. J Am Chem Soc, 2006, 128: 2385–2393

    Article  CAS  Google Scholar 

  3. Greenham NC, Peng X, Alivasatos AP. Charge separation and transport in conjugated-polymer/semiconductor-nanocrystal composites studied by photoluminescence quenching and photoconductivity. Phys Rev B Cond Matter, 1996, 54: 17628–17637

    Article  CAS  Google Scholar 

  4. Sun BQ, Marx E, Greenham NC. Photovoltaic devices using blends of branched Cdse nanoparticles and conjugated polymers. Nano Lett, 2003, 3: 961–963

    Article  CAS  Google Scholar 

  5. Sun BQ, Zou GF, Shen XJ, Zhang XH. Exciton dissociation and photovoltaic effect in germanium nanocrystals and poly(3-hexylthiophene) composites Appl Phys Lett, 2003, 94: 233504/233501–233504/233503

    Google Scholar 

  6. Kamat PV, Tvrdy K, Baker DR, Radich JG. Beyond photovoltaics: Semiconductor nanoarchitectures for liquid-junction solar cells. Chem Rev, 2010, 110: 6664–6688

    Article  CAS  Google Scholar 

  7. Kamat P. Quantum dot solar cells. Semiconductor nanocrystals as light harvesters. J Phys Chem C, 2008, 112: 18737–18753

    CAS  Google Scholar 

  8. Zhang J. Interfacial charge carrier dynamics of colloidal semiconductor nanoparticles. J Phys Chem B, 2000, 104: 7239–7253

    Article  CAS  Google Scholar 

  9. Tisdale WA, Williams KJ, Timp BA, Norris DJ, Aydil ES, Zhu X-Y. Hot-electron transfer from semiconductor nanocrystals. Science, 2010, 328: 1543–1547

    Article  CAS  Google Scholar 

  10. Sambur JB, Novet T, Parkinson BA. Multiple exciton collection in a sensitized photovoltaic system. Scienc, 2010, 330: 63–66

    Article  CAS  Google Scholar 

  11. Tachibana Y, Akiyama HY, Ohtsuka Y, Torimoto T, Kuwabata S. Cds quantum dots sensitized TiO2 sandwich type photoelectro-chemical solar cells. Chem Lett, 2007, 36: 88–89

    Article  CAS  Google Scholar 

  12. Huang J, Huang Z, Yang Y, Zhu H, Lian T. Multiple exciton dissociation in Cdse quantum dots by ultrafast electron transfer to adsorbed methylene blue. J Am Chem Soc, 2010, 132: 4858–4864

    Article  CAS  Google Scholar 

  13. Pattantyus-Abraham AG., Kramer IJ, Barkhouse A R, Wang X, Konstantatos G, Debnath R, Levina L, Raabe I, Nazeeruddin MK, Gratzel M. Depleted-heterojunction colloidal quantum dot solar cells. ACS Nano, 2010, 4: 3374–3380

    Article  CAS  Google Scholar 

  14. Plass R, Pelet S, Krueger J, Gratzel M, Bach U. Quantum dot sensitization of organic-inorganic hybrid solar cells. J Phys Chem B, 2002, 106: 7578–7580

    Article  CAS  Google Scholar 

  15. Huang J, Stockwell D, Huang Z, Mohler DL, Lian T. Photoinduced ultrafast electron transfer from CdSe quantum dots to re-bipyridyl complexes. J Am Chem Soc, 2008, 130: 5632–5633

    Article  CAS  Google Scholar 

  16. Huang J, Huang Z, Jin S, Lian T. Exciton dissociation in CdSe quantum dots by hole transfer to phenothiazine. J Phys Chem C, 2008, 112: 19734–19738

    Article  CAS  Google Scholar 

  17. Boulesbaa A, Issac A, Stockwell D, Huang Z, Huang J, Guo J, Lian T. Ultrafast charge separation at CdS quantum dot/rhodamine B molecule interface. J Am Chem Soc, 2007, 129: 15132–15133

    Article  CAS  Google Scholar 

  18. Anderson NA, Lian T. Ultrafast electron transfer at the molecule-semiconductor nanoparticle interface. Ann Rev Phys Chem, 2005, 56: 491–519

    Article  CAS  Google Scholar 

  19. Jin S, Lian T. Electron transfer dynamics from single CdSe/ZnS quantum dots to TiO2 nanoparticles. Nano Letters, 2009, 9: 2448–2454

    Article  CAS  Google Scholar 

  20. Lu HP, Xie XS. Single-molecule kinetics of interfacial electron transfer. J Phys Chem B, 1997, 101: 2753–2757

    Article  CAS  Google Scholar 

  21. Biju V, Micic M, Hu D, Lu HP. Intermittent single-molecule interfacial electron transfer dynamics. J Am Chem Soc, 2004, 126: 9374–9381

    Article  CAS  Google Scholar 

  22. Asbury JB, Hao E, Wang Y, Ghosh HN, Lian T. Ultrafast electron transfer dynamics from molecular adsorbates to semiconductor nanocrystalline thin films. J Phys Chem B, 2001, 105: 4545–4557

    Article  CAS  Google Scholar 

  23. Anderson NA, Lian T. Ultrafast electron injection from metal polypyridyl complexes to metal-oxide nanocrystalline thin films. Coord Chem Rev, 2004, 248: 1231–1246

    Article  CAS  Google Scholar 

  24. Haque SA, Park T, Holmes AB, Durrant JR. Transient optical studies of interfacial energetic disorder at nanostructured dye-sensitized inorganic/organic semiconductor heterojunctions. ChemPhysChem, 2003, 4: 89–93

    Article  CAS  Google Scholar 

  25. Gundlach L, Ernstorfer R, Willig F. Ultrafast interfacial electron transfer from the excited state of anchored molecules into a semiconductor. Prog Surf Sci, 2007, 82: 355

    Article  CAS  Google Scholar 

  26. She C, Anderson NA, Guo J, Liu F, Goh W, Chen D-T, Mohler DL, Tian Z-Q, Hupp J, Lian T. Ph dependent electron transfer from Re-bipyridyl complexes to metal oxide nanocrystalline thin films. J Phys Chem B, 2005, 109: 19345–19355

    Article  CAS  Google Scholar 

  27. She C, Guo J, Irle S, Morokuma K, Mohler DL, Zabri H, Odobel F, Youm K-T, Liu F, Hupp JT, Lian T. Comparison of interfacial electron transfer through carboxylate and phosphonate anchoring groups. J Phys Chem A, 2007, 111: 6832–6842

    Article  CAS  Google Scholar 

  28. Jin S, Snoeberger RC III, Issac A, Stockwell D, Batista VS, Lian T. Single-molecule interfacial electron transfer in donor-bridge-nanoparticle acceptor complexes. J Phys Chem B, 2010, 114: 14309–14319

    Article  CAS  Google Scholar 

  29. Gao XH, Cui YY, Levenson RM, Chung LWK, Nie SM. In vivo cancer targeting and imaging with semiconductor quantum dots. Nat Biotechnol, 2004, 22: 969–976

    Article  CAS  Google Scholar 

  30. She C, Guo J, Lian T. Comparison of electron injection dynamics from re-bipyridyl complexes to TiO2 nanocrystalline thin films in different solvent environments. J Phys Chem B, 2007, 111: 6903–6912

    Article  CAS  Google Scholar 

  31. Ushiroda S, Ruzycki N, Lu Y, Spitler MT, Parkinson BA. Dye sensitization of the anatase (101) crystal surface by a series of dicarboxylated thiacyanine dyes. J Am Chem Soc, 2005, 127: 5158–5168

    Article  CAS  Google Scholar 

  32. Sambur JB, Parkinson BA. CdSe/ZnS core/shell quantum dot sensitization of low index TiO2 single crystal surfaces. J Am Chem Soc, 2010, 132: 2130–2131

    Article  CAS  Google Scholar 

  33. Diebold U, Lehman J, Mahmoud T, Kuhn M, Leonardelli G, Hebenstreit W, Schmid M, Varga P. Intrinsic defects on a TiO2 (110) (1×1) surface and their reaction with oxygen: A scanning tunneling microscopy study. Surf Sci, 1998, 411: 137–153

    Article  CAS  Google Scholar 

  34. Nakamura R, Ohashi N, Imanishi A, Osawa T, Matsumoto Y, Koinuma H, Nakato Y. Crystal-face dependences of surface band edges and hole reactivity, revealed by preparation of essentially atomically smooth and stable (110) and (100) n-TiO2 (rutile) surfaces. J Phys Chem B, 2005, 109: 1648–1651

    Article  CAS  Google Scholar 

  35. Diebold U. The surface science of titannium dioxide. Surf Sci Rep, 2003, 48: 53–229

    Article  CAS  Google Scholar 

  36. Sasahara A, Pang CL, Onishi H. Stm observation of a ruthenium dye adsorbed on a TiO2 (110) surface. J Phys Chem B, 2006, 110: 4751–4755

    Article  CAS  Google Scholar 

  37. Nirmal M, Dabbousi BO, Bawendi MG, Macklin JJ, Trautman JK, Harris TD, Brus LE. Fluorescence intermittency in single cadmium selenide nanocrystals. Nature, 1996, 383: 802–804

    Article  CAS  Google Scholar 

  38. Krauss TD, O’Brien S, Brus LE. Charge and photoionization properties of single semiconductor nanocrystals. J Phys Chem B 2001, 105: 1725–1733

    Article  CAS  Google Scholar 

  39. Efros AL, Rosen M. Random telegraph signal in the photoluminescence intensity of a single quantum dot. Phys Rev Lett, 1997, 78: 1110–1113

    Article  CAS  Google Scholar 

  40. Shimizu KT, Woo WK, Fisher BR, Eisler HJ, Bawendi MG. Surface-enhanced emission from single semiconductor nanocrystals. Phys Rev Lett, 2002, 89: 117401/117401–117401/117404

    Google Scholar 

  41. Kuno M, Fromm DP, Johnson ST, Gallagher A, Nesbitt DJ. Modeling distributed kinetics in isolated semiconductor quantum dots. Phys Rev B, 2003, 67: 125304/125301–125304/125315

    Article  Google Scholar 

  42. Zhang K, Chang H, Fu A, Alivisatos AP, Yang H. Continuous distribution of emission states from single cdse/zns quantum dots. Nano Lett, 2006, 6: 843–847

    Article  Google Scholar 

  43. Song N, Zhu H, Jin S, Zhan W, Lian T. Poisson-distributed electron-transfer dynamics from single quantum dots to C60 molecules. ACS Nano, 2011, 5: 613–621

    Article  CAS  Google Scholar 

  44. Jin S, Song N, Lian T. Suppressed blinking dynamics of single Qds on Ito. ACS Nano, 2010, 4: 1545–1552

    Article  CAS  Google Scholar 

  45. Jin S, Hsiang J-C, Zhu H, Song N, Dickson RM, Lian T. Correlated single quantum dot blinking and interfacial electron transfer dynamics. Chem Sci, 2010, 1: 519–526

    Article  Google Scholar 

  46. Issac A, Jin S, Lian T. Intermittent electron transfer activity from single CdSe/ZnS Qds. J Am Chem Soc, 2008, 130: 11280–11281

    Article  CAS  Google Scholar 

  47. Cui S-C, Tachikawa T, Fujitsuka M, Majima T. Photoinduced electron transfer in a quantum dot-cucurbituril supramolecular complex. J Phys Chem C, 2011, 115: 1824–1830

    Article  CAS  Google Scholar 

  48. Cui S-C, Tachikawa T, Fujitsuka M, Majima T. Interfacial Electron transfer dynamics in a single CdTe quantum dot-pyromellitimide conjugate. J Phys Chem C, 2008, 112: 19625–19634

    Article  CAS  Google Scholar 

  49. Zhu H, Song N, Lian T. Controlling charge separation and recombination rates in CdSe/ZnS type I core-shell quantum dots by shell thicknesses. J Am Chem Soc, 2010, 132: 15038–15045

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Emory University, Atlanta, Georgia, 3032, USA

    ShengYe Jin & TianQuan Lian

Authors
  1. ShengYe Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. TianQuan Lian
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to TianQuan Lian.

Additional information

JIN ShengYe received his BS from Dalian University of Technology, MS from Dalian Institute of Chemical Physics, and PhD from Emory University (USA). He is currently a postdoctoral research fellow in the Center for Nanoscale Materials at Argonne National Laboratory. His research interests include single molecule/particle spectroscopy, interfacial charge transfer dynamics, plasmon enhanced photon absorption and photoluminescence, and solar energy conversion.

LIAN TianQuan (Tim) received BS from Xiamen University, MS from the Chinese Academy of Sciences, and PhD from the University of Pennsylvania. After postdoctoral training in the University of California at Berkeley, he joined the faculty of chemistry department at Emory University in 1996. He is currently the William Henry Emerson Professor in chemistry. Prof. Lian’s research interest is focused on ultrafast dynamics in photovoltaic and photocatalytic nanomaterials and at their interfaces.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Cite this article

Jin, S., Lian, T. Electron transfer dynamics of single quantum dots on the (110) surface of a rutile TiO2 single crystal. Sci. China Chem. 54, 1898–1902 (2011). https://doi.org/10.1007/s11426-011-4431-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-011-4431-7

Keywords

Search

Navigation